Process for the preparation of alkali aluminosilicate detergent builder

ABSTRACT

A detergent builder consisting essentially of an inorganic fine powder composed mainly of an alkali metal aluminosilicate having an X-ray diffraction pattern substantially the same as that of zeolite of the type A and having a degree of crystallization in the range of from 35 to 75%, wherein the inorganic fine powder has a primary particle size smaller than 1 μ and a secondary particle size smaller than 4 μ, the inorganic fine powder has a buffer capacity (S) of at least 132 ml/100 g of solids, the buffer capacity being expressed by an amount of hydrochloric acid necessary for lowering the pH of a 1% aqueous dispersion of said inorganic fine powder from 9.0 to 6.75 when the dispersion is titrated with 0.4N hydrochloric acid at a rate of 20 to 50 ml/hr, and wherein the inorganic fine powder has a calcium ion binding property (C. I.) of at least 70 mg/g as expressed as CaO.

This invention relates to a detergent builder composed of a finelydivided zeolite, which has novel characteristics, and to a process forthe preparation of this novel detergent builder. More particularly, theinvention relates to a novel finely divided alkali metal aluminosilicatebuilder having in combination an excellent alkali buffer capacity at thewashing step, an excellent metal ion sequestrating property, anexcellent re-contamination preventing property, a good dispersibility ina washing liquid and a good rinsing property, and to a novel process forproducing this builder in a high yield at a high productivity from asmectite clay mineral such as montmorillonite clay.

An alkali metal aluminosilicate such as zeolite has an excellent hardwater-softening property, namely a high calcium ion exchange capacity,and it has been long known that because of this specific property alkalimetal aluminosilicates can be used as detergent builders.

For example, the specification of Japanese Patent No. 188,551 (JapanesePatent Publication No. 1119/51) proposed by us in the past discloses aprocess comprising treating drastically acid clay or a similar clay witha mineral acid to dissolve out and remove all or substantially allcomponents other than silica and reacting the resulting activated silicawith an alkali metal aluminate to form an alkali metal polysilicate anda water-insoluble solid alkali metal aluminosilicate corresponding tozeolite.

The above specification also teaches that when the so prepared sodiumaluminosilicate is incorporated into a soap, a detergent or the like, itsoftens hard water and provides excellent emulsifiability, highpermeability, good bubbling property, good rinsing property, improvedtouch and high washing powder. It also is taught that this sodiumaluminosilicate has good compatibility and affinity with soaps and thelike.

The invention disclosed in the above patent specification is significantin the point that it reveals that a synthetic alkali metalaluminosilicate is valuable as a detergent builder. However, thespecification does not specifically disclose conditions under which analkali metal aluminosilicate builder having an optimum combination ofvarious washing-promoting properties will be obtained.

It is said that what are important among washing-promoting properties ofbuilders are a metal ion sequestrating property and a buffer capacity.Polyvalent metal ions contained in service water and stains, such asions of calcium, magnesium and iron, react with surface active agents toform hardly water-soluble salts, resulting in drastic reduction of thesurface activating capacity of detergents. Accordingly, it is importantthat detergent builders should have a property of sequestrating ions ofpolyvalent metals such as calcium, namely an ion exchange property.Greasy grimes, which must be taken into consideration at washing offibers, are composed mainly of fatty acids, triglycerides and waxes.These oil stains have a tendency to reduce the pH of a washing liquid.In order to remove stains, it is important that the pH of the washingliquid should be on the alkaline side, and when the pH of the washingliquid is reduced, it becomes difficult to remove stains for interfacialelectrical reasons. In view of the foregoing, it generally is requiredthat a substance having a buffer capacity under alkaline conditionsshould be used as a detergent builder.

Another property required of a detergent builder is that stainsextracted in the washing liquid are absorbed and fixed so as not tocause re-dissolution of the stains and so as to prevent re-contaminationof washed fibrous articles with the removed stains. In short, it isdesirable for a detergent builder to have a re-contamination preventingproperty.

Since an alkali aluminosilicate builder is water-insoluble, it isimportant that the builder should be excellent in the dispersibility ina washing liquid and the rinsing property. All the actions of awater-insoluble solid builder are performed through the contactinterface between the builder and the washing liquid. Accordingly, asthe solid builder is uniformly and homogeneously dispersed in thewashing liquid and as the surface area per unit weight is large, theabove-mentioned characteristics such as the metal ion sequestratingproperty, buffer capacity and re-contamination preventing property aremanifested more conspicuously. When the dispersibility of awater-insoluble solid builder is insufficient, the solid builder tendsto adhere to washed articles and to reduce the rinsing property, andsuch troubles as so-called "powder falling" which is a phenomenon thatbuilder powder falls from a dried washed article are often caused.

When a solid builder is composed of coarse particles, sedimentation ordeposition of builder particles takes place in pipes for dischargingwashing liquids and such troubles as clogging of tubes and wearing oftube walls are caused.

In view of the foregoing, it is preferred that an alkali aluminosilicatebuilder be composed of particles as fine as possible. However, anindustrial process capable of providing fine particles of an alkalialuminosilicate has not been developed in the art. For example, JapanesePatent Application Laid-Open Specification No. 12381/75 discloses thatan aluminosilicate compound in which at least 80% by weight of particleshave a size of 10 to 0.01 μ, preferably 8 to 0.1 μ, can be used as abuilder, and Japanese Patent Application Laid-Open Specification No.53404/75 discloses that an inorganic aluminosilicate ion exchangematerial having a particle size of about 0.1 to about 100 μ, especially0.2 to 10 μ, can be used as a builder. However, in a specific embodimentof the former laid-open specification, only an alkali aluminosilicate inwhich most of particles have a primary particle size of 1 to 3 μ isobtained, and in a specific embodiment of the latter laid-openspecification, only an alkali aluminosilicate composed of particleshaving an average primary particle size of 3 to 5 μ is obtained. Namely,it is apparent that though it is desirable to use an alkali metalaluminosilicate builder having a smaller particle size, it has been verydifficult for experts in the art to synthesize an alkali metalaluminosilicate having a primary particle size smaller than 1 μ.

This invention relates to an improvement in the alkali metalsaluminosilicate builder disclosed in the above-mentioned Japanese Pat.No. 188,551. More specifically, this invention provides a detergentbuilder composed of a zeolite in which substantially all of theparticles have a primary particle size smaller than 1 μ, which has incombination a high alkali buffer capacity, an excellent metal ionsequestrating property, a high re-contamination preventing property anda good dispersibility into a washing liquid, and the invention furtherprovides a process for preparing this excellent detergent builder.

We found that in the process for preparing a zeolite builder fromactivated silica or activated aluminosilicic acid obtained by the acidtreatment of a smectite clay, when the activated silica or activatedalumina-silica is subjected to the pre-treatment with a caustic alkalior water-soluble alkali metal silicate and an alkali metal polysilicateor alkali metal polyaluminosilicate having a specific composition isprepared prior to the synthesis of zeolite, a finely divided zeolite inwhich substantially all of the particles have a primary particle sizesmaller than 1 μ can be obtained and this finely divided zeolite issuperior or at least comparable to known zeolites with respect to themetal ion sequestrating property and is conspicuously excellent in suchproperties as buffer capacity, re-contamination preventing property anddispersibility in a washing liquid. Based on this finding, we have nowcompleted this invention.

More specifically, in accordance with this invention, there is provideda detergent builder consisting essentially of an inorganic fine powdercomposed mainly of an alkali aluminosilicate having an X-ray diffractionpattern substantially the same as that of zeolite of the type A andhaving a degree of crystallization in the range of from 35 to 75%,wherein said inorganic fine powder has a primary particle size smallerthan 1 μ and a second particle size smaller than 4 μ, said inorganicfine powder has a buffer capacity (S) of at least 132 ml/100 g ofsolids, said buffer capacity being expressed by an amount ofhydrochloric acid required for lowering the pH of a 1% aqueousdispersion of said inorganic fine powder from 9.0 to 6.75 when saiddispersion is titrated with 0.4N hydrochloric acid solution at a rate of20 to 50 ml/hr, and wherein said inorganic fine powder has a calcium ionbinding property (C.I.) of at least 70 mg/g as expressed as CaO.

In accordance with this invention, there also is provided a process forthe preparation of detergent builders which comprises acid-treating asmectite clay mineral under such conditions that at least the X-raydiffraction peak of the plane index [001] substantially disappears, tothereby prepare activated silicic acid or activated aluminosilicic acid,treating the so prepared activated silicic acid or activatedaluminosilicic acid with an alkali metal hydroxide or a water-solublealkali metal silicate to prepare an alkali metal polysilicate or alkalimetal polyaluminosilicate having a composition in which the Na₂ O/SiO₂molar ratio is in the range of from 1/3.5 to 1/500, mixing said alkalimetal polysilicate or alkali metal polyaluminosilicate with additionalamounts of alumina and alkali metal components and water to prepare ahomogeneous mixture having a composition capable of forming zeolite ofthe type A, and heating said homogeneous mixture to crystallize out finezeolitic particles having a primary particle size smaller than 1 μ.

This invention will now be described in detail by the followingdescription and the accompanying drawings in which:

FIG. 1 illustrates the arrangement of apparatus measuring buffercapacity;

FIG. 2 illustrates a titration curve for alkali metal aluminosilicatewith hydrochloric acid;

FIG. 3 illustrates a hydrochloric acid titration curve of commerciallyavailable zeolite of type 4A;

FIG. 4 illustrates a titration curve of a homogeneous mixture ofcommercially available zeolite and sodium hydroxide;

FIG. 5 illustrates a titration curve of the building of this inventionobtained in Example 1;

FIG. 6 illustrates an electron-microscope photograph of commerciallyavailable zeolite of the type 4A;

FIG. 7 illustrates an electron-microscope photograph of the zeolitebuilder of this invention;

FIG. 8 illustrates an X-ray diffraction pattern of acid clay rawmaterial;

FIG. 9 illustrates an X-ray diffraction pattern of aluminasilicateaccording to Example 5;

FIG. 10 illustrates an X-ray diffraction pattern of alumina-silicaobtained in Example 5; and

FIG. 11 illustrates an X-ray diffraction pattern of anotheralumina-silica obtained in Example 5.

CHEMICAL STRUCTURE OF ALKALI METAL ALUMINOSILICATE BUILDER

In general, the alkali metal aluminosilicate builder of this inventionhas a chemical composition (% by weight) shown in Table A given below.

                  Table A                                                         ______________________________________                                        Chemical Composition (% by weight) (as deter-                                 mined with sample dried at 110° C.)                                            Ordinary Range                                                                             Preferred Range                                          ______________________________________                                        SiO.sub.2 35 - 45        36 - 40                                              Al.sub.2 O.sub.3                                                                        25 - 35        27 - 33                                              Na.sub.2 O                                                                              13 - 20        14 - 19                                              ignition loss                                                                           14 - 18        15 - 17                                              Fe.sub.2 O.sub.3                                                                        below 3        below 1                                              CaO       below 3        below 0.1                                            MgO       below 3        below 0.1                                            ______________________________________                                    

This alkali metal aluminosilicate builder is composed mainly of awater-insoluble crystalline sodium aluminosilicate represented ideallyby the following formula:

    Na.sub.12 (Al.sub.12 Si.sub.12 O.sub.48).15-30H.sub.2 O

and it contains minute amounts of an amorphous alkali metalpolysilicate, aluminum polysilicate or alkali metal aluminosilicate andcrystalline polysilicic acid materials as impurities within such a rangeas will satisfy the requirement of the degree of crystillizationdescribed hereinafter.

STRUCTURE AND PROPERTIES OF ALKALI ALUMINOSILICATE BUILDER

The water-insoluble inorganic powdery builder of this invention has anX-ray diffraction pattern indicated in Table B given hereinafter.Namely, it has an X-ray diffraction pattern substantially the same asthat of zeolite of the type A. The X-ray diffraction pattern referred toin the instant specification and claims means one determined by thefollowing X-ray diffraction method using Cu-Kα rays.

(i) Method for determination of X-ray diffraction pattern:

An X-ray diffraction apparatus manufactured by Rigaku Denki K. K. (X-raygenerator Model Cat. No. 2171L and goniometer Model Cat. No. 4001) isused for the determination. Conditions adopted are as follows:

Target: Cu

Filter: Ni

Voltage: 30 KV

Current: 15 mA

Count Full Scale: 500 C/S

High Voltage: 1200 V

Time Constant: 2 seconds

Chart Speed: 2 cm/min

Scanning Speed: 2°/min

Divergency: 1°

Receiving Slit Width: 0.3 mm

Each sample is first dried in a drier maintained at 110° C. andpulverized in an agate mortar, and it is then used for the measurement.

                  Table B                                                         ______________________________________                                        X-Ray Diffraction Pattern                                                     Spacing d (KX)  Relative Intensity (I/I.sub.o)                                ______________________________________                                        12.440          65.3                                                          8.750           58.5                                                          7.132           48.3                                                          5.534           41.6                                                          4.371           17.8                                                          4.111           60                                                            3.720           95.8                                                          3.421           33                                                            3.300           81.4                                                          2.986           100                                                           2.910           24.6                                                          2.753           27.2                                                          2.627           70.4                                                          2.513           13.6                                                          2.466           11.0                                                          ______________________________________                                    

In the instant specification and claims, by the term "X-ray diffractionpattern substantially the same as the above X-ray diffraction pattern "is meant an X-ray diffraction pattern in which the relative intensity ofeach diffraction peak can be changed from the above-indicated valuewithin a certain range, generally within ± 30%, especially within ± 20%.

In the alkali metal aluminosilicate builder of this invention, the orderof the intensity is sometimes changed depending on the kind of the solidpolysilicate used for the synthesis. For example, when a highlyacid-treated clay mineral is used as the starting solid polysilicate,the intensity of the peak of the spacing d of 12.440 KX is higher thanthe intensity of the peak of the spacing d of 8.750 KX, but it is foundthat this order is reversed when a lowly acid-treated clay mineral isused. Further, when a small amount of a sodalite hydrate crystalstructure is present in the alkali metal aluminosilicate builder, theorder of the intensity between the peak of the spacing d of 2.986 KX andthe peak of the spacing d of 3.720 KX is reversed.

Since the alkali aluminosilicate builder of this invention is derivedfrom a smectite clay mineral, it occasionally has, in addition to theabove-mentioned X-ray diffraction peaks, those inherent of the startingclay mineral. It is often observed that the alkali aluminosilicatebuilder formed by using acid-treated acid clay shows small peaksinherent of substances contained in this starting raw clay, for example,quartz (d = 3.343 KX), cristobalite (d = 4.05 KX) and feldspar (d =3.7697 and 3.1977 KX). When the akali aluminosilicate builder of thisinvention has a relatively low value of the degree of crystallizationdescribed hereinafter, it is characterized in that its X-ray diffractionpattern has small peaks such as mentioned above.

It is known that crystalline alkali aluminosilicates, especiallyzeolites, include various kinds differing in the chemical structure, forexample, synthetic zeolites of types A, X, Y and T, chabazite,mordenite, erionite, faujasite, clinoptilolite and sodalite hydrate. Thealkali aluminosilicate having the above-mentioned X-ray diffractionpattern, that is used in this invention, is one known as zeolite of thetype A.

In the builder of this invention, in order to enhance thewashing-promoting activity, it is important that an alkalialuminosilicate having a structure of the type A zeolite is especiallychosen among various zeolites. It is said that important characteristicsof the builder for promoting the washing are the metal ion sequestratingproperty and the buffer capacity. Ions of polyvalent metals contained inservice water or stains, such as ions of calcium, magnesium and iron,react with a surface active agent in a detergent to form hardlywater-soluble salts, and hence, they drastically reduce the surfaceactivating property of the detergent. Accordingly, it is important thatthe detergent builder should have a property of sequestering ions ofpolyvalent metals such as calcium, namely an ion exchange property.Theoretical ion exchange capacities of various zeolites are as shown inTable C given hereinafter. From these data, it will readily beunderstood that an alkali metal aluminosilicate of the type A zeolite,which is especially chosen in this invention, is excellent in the metalion sequestrating property.

                  Table C                                                         ______________________________________                                        Ion Exchange Capacity (milli-equivalent/g)                                             Ion Exchange Capacity                                                                         Ion Exchange Capacity                                Zeolite  (based on anhydride)                                                                          (based on hydrate)                                   ______________________________________                                        chabazite                                                                              5               3.9                                                  mordenite                                                                              2.6             2.3                                                  erionite 3.8             3.1                                                  clinoptilolite                                                                         2.6             2.2                                                  zeolite A                                                                              7.0             5.5                                                  zeolite X                                                                              6.4             4.7                                                  zeolite Y                                                                              5.0             3.7                                                  zeolite T                                                                              3.4             2.8                                                  ______________________________________                                    

Although the builder of this invention is synthesized from a naturallyoccurring smectite clay mineral as the raw material, it has a metalsequestrating property superior or at least comparable to that of aknown synthetic zeolite prepared from a synthetic alkali silicatesolution. The metal ion sequestrating property can be determinedaccording to the following measurement method.

(ii) Method for determination of calcium ion binding property (C.I.):

A calcium-containing solution having a calcium concentration of 300 mg/l(D.H. 30) as CaO is prepared and 500 ml of the so prepared solution istaken into a beaker having a capacity of 1 liter and is heated at 30° C.Then, 0.500 g of a sample which has been dried for 2 hours in a driermaintained at 110° C. previously and naturally cooled to roomtemperature in a desiccator is precisely weighed by a constantsensibility direct-reading balance and poured into thecalcium-containing solution. The mixture is agitated in a jar tester for20 minutes at an agitation rate of 120 rpm to thereby cause the sampleto perform exchange of calcium ion. Then, the mixture is filtered by afilter paper No. 6 and precisely measured 10 ml of the filtrate iscollected and diluted with deionized water to form about 50 ml of adiluted solution. Then, 4 ml of 8N KOH is added to the solution toadjust the pH to 12, and several drops of 5% KCN are added and 0.1 g ofNN indicator is further added. Then titration is carried out by using anEDTA solution having a concentration of 1/100 mole/l to determine theCaO concentration, and the calcium ion binding property is calculatedaccording to the following equation:

Calcium ion binding property (mg/g) = 300 - 56BF wherein B denotes theamount (ml) of the EDTA solution having a concentration of 1/100 mole/lwhich is used for titration and F represents the factor of the EDTAsolution having a concentration of 1/100 mole/l.

The alkali aluminosilicate builder of this invention has generally acalcium binding property of at least 70 mg/g, preferably 90 to 160 mg/g,though the value is changed to some extent according to such factors asthe kind of the starting raw clay mineral, the acid treatment conditionsand the conditions for crystallizing out the zeolite. The theoreticalvalue of the calcium binding property of zeolite A is 152 mg/g based onthe hydrate. It is quite surprising that the builder of this inventionhas a calcium binding property value very close to this theoreticalvalue even if the degree of crystallization described hereinafter isconsiderably low.

In view of the calcium binding property, it is important that thebuilder of this invention should have a degree of crystallization of atleast 35%, especially at least 55%. Further, in view of the buffercapacity described hereinafter and the control of keeping the surfacepotential of particles negative after exchange of calcium ion, it ispreferred that the degree of crystallization be not higher than 75%,especially not higher than 70%.

In the instant specification and claims, by the term "degree ofcrystallization" is meant a value determined according to the followingmethod.

(iii) Method for determination of degree of crystallization (C.R.):

(a) The X-ray diffraction curve of a sample is determined according tothe above-mentioned powder X-ray diffraction method.

(b) Points of diffraction angle 2θ = 9° and 2θ = 39° in the X-raydiffraction curve are connected by a straight line. This line isdesignated as the base line.

(c) Two lowermost points among troughs between every two adjacent peaks(except those in which the distance between two diffraction peak skirtsis smaller than 1°) are connected by a straight line. This line isdesignated as the amorphous line.

(d) The degree (%) of crystallization is calculated according to thefollowing formula: ##EQU1## wherein S_(A) represents an area between thebase line and amorphous line and S_(C) denotes an area between theamorphous line and the diffraction curve.

In the case where the X-ray diffraction pattern includes diffractionpeaks of quartz, cristobalite, feldspar and the like and the degree ofcrystallization toward zeolite is relatively low, crystalline portionsother than the zeolite portion are inclusively calculated and theobtained value of the degree of crystallization is a little higher thanthe actual value. This difference, however, causes no substantialproblem when comparison is made based on such values.

Commercially available synthetic zeolite of the type A has a degree ofcrystallization higher than 75%, when determined according to theabove-mentioned method. This known synthetic zeolite of the type Ahaving a degree of crystallization higher than 75% is insufficient inthe buffer capacity and other properties as is seen from sample H-1shown in Comparative Example 1 given hereinafter.

Since the alkali metal aluminosilicate builder of this invention issynthesized from a smectite clay mineral and has a degree ofcrystallization in the above-mentioned range, it can possess a buffercapacity (S) of at least 132 ml/100 g of solids, preferably at least 136ml/100 g of solids, especially preferably at least 140 ml/100 g ofsolids. In the instant specification and claims, the buffer capacity (S)is defined as an amount (ml/100 g of solids) of hydrochloric acidnecessary for lowering the pH of a 1% aqueous dispersion of a samplefrom 9.0 to 6.75 when the dispersion is titrated with 0.4N hydrochloricacid at a rate of 20 to 50 ml/hr. More specifically, this value isdetermined according to the following method.

(iv) Method for determination of buffer capacity (S) and initial buffercapacity (R):

Referring now to FIG. 1 illustrating the arrangement of an apparatus formeasuring the buffer capacity, a 1% aqueous dispersion of a sample ischarged in a vessel 2 equipped with a magnetic stirrer in an amountcorresponding to 3 g of solids in the dispersion.

A glass electrode 3 is immersed in this dispersion and this electrode isconnected to a pH meter 4. The output terminal of the pH meter 4 isconnected to a recorder 5 and the detected pH value is recorded on arecording paper 6.

Separately, 0.4N solution of hydrochloric acid is charged in a vessel 7,and this hydrochloric acid is added dropwise to the aqueous dispersionin the vessel 2 at a constant rate through a metering pump 8 and aconduit 9.

The instruments and conditions used and adopted for the measurement areas follows:

pH meter: model HM-5A manufactured by Toa Denpa K. K.

Recorder: model QPD-53 53 manufactured by Hitachi Seisakusho K. K., fullscale = 50 mV, chart speed = 240 mm/hr

Constant flow pump: manufactured by Nisshin Kagaku K. K., hydrochloricacid pouring rate = 37 ml/hr

A typical instance of the curve of titration of the alkali metalaluminosilicate with hydrochloric acid is shown in FIG. 2, in which theordinate denotes the pH value and the abscissa denotes the amounttitrated of hydrochloric acid (ml/100 g of solids). The followingcharacteristics can be determined from this titration curve.

(a) Buffer capacity (S):

The buffer capacity (S) is expressed as the amount of hydrochloric acidrequired for lowering the pH from 9.0 to 6.75. Namely, the buffercapacity (S) is calculated according to the following formula:

    S= V.sub. 6.75 - V.sub.9

wherein V₉ denotes the amount (ml/100 g of solids) of hydrochloric acidrequired for lowering the pH of the above-mentioned dispersion to 9.0and V₆.75 denotes the amount (ml/100 g of solids) of hydrochloric acidrequired for lowering the pH of the above-mentioned dispersion to 6.75.

(b) Initial buffer capacity (R):

The initial buffer capacity (R) is expressed as the amount ofhydrochloric acid required for lowering the pH from 9.0 to 8.0. Namely,the initial buffer capacity (R) is calculated according to the followingformula:

    R = V.sub. 8 - V.sub.9

wherein V₉ is as defined above and V₈ denotes the amount (ml/100 g ofsolids) of hydrochloric acid required for lowering the pH of theabove-mentioned dispersion to 8.0.

(c) Effective alkali quantity (Q_(c)):

The effective alkali quantity is expressed as the total amount ofhydrochloric acid required for lowering the pH of the above-mentioneddispersion to 6.75. More specifically, the concentration (Q_(c), %) ofthe effective alkali in the builder as NaOH can be calculated from theV₆.75 value according to the following formula:

    Q.sub.c = 1.60 × 10.sup.-2 V.sub.6.75

as is apparent from FIG. 2, at the initial stage of titration withhydrochloric acid, the pH of the aqueous dispersion is almost constant,and with advance of titration, the pH begins to decrease abruptly. Thereason why the buffer capacity is defined as the amount of hydrochloricacid required for lowering the pH from 9.0 to 6.75 in this invention isas follows:

In order to attain a good washing effect, it is important that the zeta(ζ) potential of fibers or stains in the washing liquid should beincreased in the negative direction, and in order to control this zetapotential forcibly on the negative side, it is preferred that the pH ofthe washing liquid be maintained on the alkaline side, namely at a levelhigher than 6.75, irrespective of acidic substances contained in stainsand the like.

When the builder per se has a pH value considerably higher than 9.0,fibers are readily damaged by the washing liquid. Accordingly, it isdesirable for the builder to show a high resistance to lowering of thepH in the range of from a relatively lowly alkaline pH of 9.0 to theabove-mentioned critical pH level of 6.75. In view of the foregoing, inthis invention, the buffer capacity is defined as the amount ofhydrochloric acid required for lowering the pH from 9.0 to 6.75. Thehigher the buffer capacity, the higher is the buffer action of thedetergent builder, and an excellent washing-promoting action can beattained by a builder having a high buffer capacity. As will be apparentfrom the foregoing illustration, a detergent composition comprising abuilder having a buffer capacity within the range specified in thisinvention is characterized in that reduction of the washing power isremarkably controlled and is advantageous in that larger quantities ofarticles can be washed with use of a much reduced amount of thedetergent.

In order to effectively remove heavy stains from articles or materialsto be washed, it is preferred that the above-mentioned initial buffercapacity (R) of the builder of this invention be at least 35 ml/100 g ofsolids, especially at least 40 ml/100 g of solids.

In the builder of the present invention, the abovementioned effectivealkali quantity (Q_(c)) is ordinarily in the range of from 2 to 8%,especially 3 to 6%, though this effective alkali amount (Q_(c)) differsto some extent depending on the crystal structure or composition of thezeolite.

FIG. 3 illustrates a hydrochloric acid titration curve of commerciallyavailable zeolite of the type 4A (manufactured by Tekkosha K.K.), fromwhich it will readily be understood that the known zeolite has anextremely low buffer capacity (S = 69.1).

FIG. 4 illustrates a titration curve of a homogeneous mixture of theabove-mentioned commercially available zeolite and sodium hydroxide. Inthis composition, the effective alkali quantity (Q_(c)) is much largerthan in case of the zeolite shown in FIG. 3, but in case of thiscomposition, it will readily be understood that the amount of the freealkali bringing about a pH higher than 9, namely the V₉ value, isextremely increased and the buffer capacity (S) is still at such a lowlevel as 67 ml/100 g of solids.

In contrast, as will be apparent from FIG. 5 illustrating a titrationcurve of the builder of this invention obtained in Example 1 givenhereinafter, since the builder is derived from a smectite clay mineral,it has such a high biffer capacity (S) as 150.4 ml/100 g of solids.

In alkali metal aluminosilicate builders, in general, it is construedthat a part of the alkali metal component is present in the form of acrystalline alkali aluminosilicate, another part of the alkali componentis present in the form of an alkali hydroxide or a water-soluble alkalimetal salt and still another part of the alkali metal component ispresent in the alkalized state. As the term "hydrated state" indicatesthe state where dissolved or dispersed particles are combined withmolecules of water or dissolved or dispersed particles and molecules ofwater have mutual actions with each other, in the instant specificationthe term "alkalized state" is used to mean the state where dispersedparticles of the alkali metal aluminosilicate are combined with alkalimetal ions or the dispersed particles and alkali metal ions have mutualactions with each other. Since the alkali aluminosilicate per sereleases an alkali metal component, according to customary analysismeans it is difficult to determine in what state the alkali component ispresent, though only the alkali metal component present in the freestate can be determined. It is construed that the reason why the zeoliteof this invention synthesized from a smectite clay mineral as thestarting material has a particularly high buffer capacity (S) is thatthe alkali metal component is not present in the form of a free alkalior a crystalline alkali aluminosilicate but in an intermediate state,namely in the above-mentioned "alkalized" state.

By virtue of the above-mentioned neutralization or titrationcharacteristic, the alkali aluminosilicate builider of this inventionhas such a property that when a 1% aqueous dipersion of the alkalialuminosilicate of this invention is boiled for 5 minutes, the pH of theboiled dispersion is ordinarily in the range of from 9.5 to 12,especially preferably in the range of from 9.8 to 11.5.

The alkali aluminosilicate builder of this invention has a novel featurethat the primary particle size is smaller than 1 μ and the secondaryparticle size is smaller than 4 μ. As pointed out hereinbefore, pg,26according to known methods, it is extremely difficult to prepare asynthetic zeolite builder in which substantially all of the particleshave a primary particle size smaller tha 1 μ. According to thisinvention, in contrast, such finely divided zeolite can easily beprepared and the dispersibility of the builder into water can beremarkably improved. As a result, according to this invention, it ispossible to maintain the metal ion sequestrating property, the alkalibuffer capacity and the re-contamination preventing effect at very highlevels stably for a long time. Moreover, the rinsing property can beremarkably improved and troubles such as powder falling can beeffectively prevented.

In the instant specification and claims, by the term "primary particlesize" is meant a minimum size of the cubic particle of a zeolite, namelya length of edge of the cubic zeolite particle, observed on anelectron-microscopic photography. More specifically, the primaryparticle size is determined according to the following method.

(v) Method for measurement of primary particle size (D_(p)):

In the instant specification, the "primary particle size" means a lengthof edge of cubic particles directly measured by an electron microscopein the state where respective particles are well dispersed. Themeasurement is performed according to the following method.

A suitable amount of a sample is placed on a glass sheet, and paraffinwax or vaseline in a volume substantially equal to the volume of thesample is added to the sample. The mixture is sufficiently kneaded by asmall stainless steel spatula, and a small amount of ethanol is furtheradded and the mixture is further kneaded. The kneaded mixture is placedon a mesh for electron-microscopic measurement and immersed in ethanolto dissolve out the paraffin or the like. Then, the sample is dried for1 hour in a drier maintained at 60° to 70° C. to evaporate ethanol.

According to customary procedures, 4 electronmicroscopic photographssuitable for the measurement of the primary particle size are taken fromdifferent vision fields at a magnification of 1,000 to 2,000 and thephotographs are enlarged 10 times to obtain photographs having a totalmagnification of 10,000 to 20,000.

Among cubic particles taken on these photographs, 6 typical particlesare chosen and among sides or edges of these particles, those deemed tobe in parallel to the plane of the vision field (the mesh plane) arechosen and the length of each of these sides is measured. The maximumvalue among the measured values is designated as the primary particlesize (D_(p)) referred to in the instant specification.

FIG. 6 illustrates an electron-microscopic photograph of commerciallyavailable zeolite of the type 4A, and FIG. 7 illustrates anelectron-microscopic photograph of the zeolite builder of thisinvention. From these FIGS., it will readily be understood that thebuilder of this invention has a remarkably fine primary particle sizeand is very excellent with respect to the uniformity of the particlesize.

In the builder of this invention, not only the primary particle size isremarkably fine but also the size of practical powder, namely thesecondary particle size, is remarkably fine and is smaller than 4 μ. Inthe instant specification and claims, the secondary particle size is onethat is determined according to the following method for measurement ofthe particle size distribution.

(vi) Method for measurement particle size distribution:

The measurement is carried out by using an apparatus of the lightscanning type for prompt measurement of the particle size distribution(model PSA-2 manufactured by Hitachi Seisakusho K.K.). Particles aresuspended in a liquid, and the suspension is agitated to disperse theparticles uniformly. Dispersed particles are sedimented with the lapseof time according to Stokes' law and the particle concentrationdistribution is generated in the liquid because of the difference ofparticle sizes. The particle size distribution is determined byutilizing this principle. Namely, the particle concentrationdistribution is optically measured after a certain period of time haspassed from dispersing of the particles and is electrically recorded byconverting optical signals to electric signals. Practical measurementprocedures are as follows:

In a corked test tube (having a capacity of 10 ml) is charged 20 mg of asample, and 5 ml of a 0.1% solution of sodium hexametaphosphate isadded. The corked test tube is attached to a shaking device and thecontent is shaken at a rate of about 60 reciprocations per minute for 30minutes to disperse the sample in the sodium hexametaphosphate solution.The dispersion is transferred into a measurement cell (8.5 cm in height,2.0 cm in length and 2.0 cm in width), and deionized water is poureduntil the liquid level reaches precisely a standard line (50 ml). Thecell is then set to the measurement apparatus, and the content of thecell is sufficiently stirred by an agitation rod and is then allowed tostand still. Simultaneously with stopping of the agitation, a stop-watchis actuated. Then, the apparatus is actuated to draw a particle sizedistribution curve and an approximate measurement time is examined. Thisoperation is performed to know whether or not it is possible to obtainprecise values. If deionized water has not been added precisely to thestandard line, the top portion of the obtained curve is disturbed andprecise values cannot be obtained. When it is confirmed by the abovepreliminary operation that a precise curve will be obtained, anautomatic recorder is actuated to draw a particle size distributioncurve. The measurement time and the density and viscosity of the liquidhave been read in advance from a calculating table. Further, theparticle size of the sample is calculated from a prescribed calculatingpaper. The recorded curve is divided in equal portions according to theso calculated particle size and the intensity of transmitted light onthe dividing point of the curve is read and log I is then read from alogarithmic conversion scale. Based on the read value, the particle sizedistribution is calculated from a prescribed calculating paper.

In the instant specification, by the expression "3 - 4 μ (%)" is meant %by weight of particles having a size larger than 3 μ and not larger than4 μ.

Since both the primary particle size and the secondary particle size arevery fine in the finely divided zeolite of this invention, it has a veryexcellent water-dispersibility and shows a very high suspensionstability when it is actually used for washing in the state incorporatedin a detergent composition. The water-dispersibility can be evaluatedbased on a rate of formation of a supernatant, namely a sedimentationspeed, observed when an aqueous dispersion having a prescribedconcentration is allowed to stand still. When the sedimentation speed ofcommercially available zeolite powder or of a zeolite obtained accordingto a known synthesis method is measured according to the measurementmethod described below, the sedimentation speed is higher than 9.4 cm/hrin any case. In contrast, the sedimentation speed of the zeolite builderof this invention, determined according to the same measurement method,is lower than 4 cm/hr. Thus, it is apparent that the builder of thisinvention is very excellent in the dispersibility and dispersionstability.

(vii) Method for measurement of sedimentation speed:

A sample is appropriately dried to reduce the water content to 5 to 6 %,lightly pulverized in an agate mortar and passed through a sieve of 200Tyler mesh.

The pulverized sample is dried for 2 hours in a drier maintained at 110°C. and naturally cooled to room temperature in a desiccator to form atest sample.

By a precision balance, 0.500 g of the test sample is weighed and addedto 1000 ml (± 1 ml) of deionized water maintained at 20° ± 2° C., andthe mixture is agitated at a rate of 120 rpm in a jar tester for 5minutes to form a suspension. The concentration of the so formedsuspension is 0.05 %.

After the above agitation conducted for 5 minutes in the jar tester, thesuspension is immediately pured into a 100-ml graduated cylinder havinga height of 22.5 cm and a diameter of 2.6 cm to a standard lineindicating 100 ml (the height of this standard line is 18.7 cm from thebottom). When 30 minutes have passed from completion of the abovepouring operation, the height (cm) of the layer of the supernatant ismeasured and the value of the sedimentation speed (cm/hr) is determinedby multiplying the measured height value by 2.

Since the builder of this invention is composed of water-insoluble veryfine particles, it has a high Methylene Blue-adsorbing property. By theterm " Methylene Blue-adsorbing property " referred to in the instantspecification and claims is meant a property of adsorbing Methylene Bluedye dissolved in water, and this property is evaluated according to thefollowing measurement method. This Methylene Blue-adsorbing property isclosely concerned with the stain-adsorbing property and hence, with there-contamination preventing property of the builder.

(viii) Method for measurement of Methylene Blue-adsorbing property (AM):

(a) Preparation of test sample:

By a precision balance, 0.2 g of a sample is weighed, and it issuspended in 30 ml of deionized water at room temperature (20°± 2° C.),and the hydrogen ion concentration (pH) of the suspension is measured bya glass electrode type pH meter (model HM-5A manufactured by Toa DenpaK. K.) The pH is adjusted to 10.5 ± 0.2 by addition of a 0.1N solutionof sodium hydroxide (NaOH) or a 0.1N solution of hydrochloric acid(HCl). Then, 50 ml of a 8 ppm solution (pH = 10.5 ) of Methylene Blue EP(C₁₆ H₁₈ N₃ SCl·nH₂ O) is added to the suspension. The mixture is shakenat a shaking rate of 140 reciprocations per minute and stroke of 8 cmfor 15 minutes by a shaking machine. Then, the suspension is filtered bya filter paper No. 6 (specified by JIS) and the filtrate is used as atest sample. The measurement is carried out within 120 minutes fromcompletion of the preparation of the test sample.

(b) Preparation of standard dye solutions for colorimetry:

By a precision balance, 1.000 g of Methylene Blue EP (C₁₆ H₁₈ N₃ SCl·nH₂O) is weighed, and it is then charged in a graduated cylinder having acapacity of 1 liter. A dye solution having a concentration of 0.1 % isfirst prepared and it is then diluted to a concentration of 5 ppm, 1.67ppm, 0.57 ppm or 0.278 ppm. These diluted dye solutions and deionizedwater are separately charged in colorimetric test tubes having adiameter of 25 mm, a length of 250 mm and a capacity of 100 ml.Chromatocities of the 5 ppm dye solution, 1.67 ppm dye solution, 0.577ppm dye solution, 0.278 ppm dye solution and deionized water(transparent) are designated as 1, 2, 3, 4 and 5, respectively.

(c) Measurement method:

The test sample solution prepared above is charged in a test tube havinga diameter of 25 mm and a length of 250 mm, and the color of thesolution is compared with colors of the above 5 standard solutions underwhite light with the naked eye to determine the color concentrationcorresponding to the color concentration of the test sample solution. Ifthe color of the sample solution is intermediate between colors of twostandard solutions, the chromatocity is expressed as 1.5, 2.5, 3.5 or4.5. Accordingly, when the test sample solution has a higher value ofthe chromatocity, it has a higher Methylene Blue-adsorbing property.

Since the builder of this invention has a very fine primary particlesize, it has a very large surface area per unit weight and the capacityof adsorbing and retaining oil stains or geasy grimes is extremely high.This surface area characteristic can be evaluated by the bulk densityand the oil absorption.

The builder of this invention has an oil absorption of at least 45ml/100 g of the sample, especially at least 48 ml/100 g of the sample,as measured according to the following method, and it has a bulk densitynot higher than 0.5 g/cc, especially not higher than 0.48 g/cc, asmeasured according to the method described below.

(ix) Method for measurement of oil absorption (O.A.):

A sample is appropriately dried to reduce a water content to 5 to 6 %,lightly pulverized in an agate mortar and passed through a sieve of 200Tyler mesh.

The pulverized sample is dried for 2 hours in a drier maintained at 110°C. and naturally cooled to room temperature in a desiccator to form atest sample.

By a precision balance, 1.000 g of the test sample is weighed, and it isplaced on a glass sheet. Refined linseed oil (first grade; manufacturedby Wako Junyaku K. K.) is added to the center of the test sample littleby little through a buret (minimum graduation = 0.01 ml) and every timeone drop of linseed oil is added, the entire sample is kneaded by aspatula. This operation is repeated until the entire mixture is formedinto one mass resembling a putty and it can be wound in a film-like formby the steel spatula. The volume (ml) of added refined linseed oil ismultiplied by 100 and the obtained value is designated as the oilabsorption (O.A.) (ml/100 g of the sample).

(x) Method for measurement of bulk density:

A sample is appropriately dried to reduce the water content to 5 to 6 %,lightly pulverized in an agate mortar and passed through a sieve of 200Tyler mesh.

The pulverized sample is dried for 2 hours in a drier maintained at 110°C. and naturally dried to room temperature in a desiccator to form atest sample.

The bulk density is determined according to the so called iron cylindermethod using iron cylinder and plunger described below. A plunger iscorrectly let to fall naturally into a clean cylinder and the height(H_(o) ) of the upper projecting portion of the plunger is read (to theorder of 1/10 mm).

Then, the plunger is taken out, and 1.00 g of the test sample weighed bya precision balance is quietly poured into the cylinder while preventingscattering of the test sample. The sample adhering to the wall face ofthe cylinder is let to fall by lightly moving the cylinder or impartinga light shock to the cylinder, and the level of the test sample in thecylinder is thus made flat. Then, the plunger is gently and correctlylet to fall into the cylinder from above while lightly supporting theplunger with the fingers.

In principle, the time required for the plunger to reach the level ofthe test sample in the cylinder is set as 5 seconds. When the plungerreaches the sample level, the plunger is caused to make one rotationwhile lightly supporting the plunger with the fingers so that theplunger gets intimate with the test sample.

The plunger is allowed to stand in this state for 5 minutes, and theheight (H) of the upper projecting portion is read and the bulk density(B.D.) is calculated according to the following formula: ##EQU2##wherein B.D. stands for the bulk density, H_(o) designates the length(cm) of the projecting portion of the plunger before packing of the testsample, H stands for the length (cm) of the projecting portion of theplunger in the presence of the test sample, and S denotes the weight (g)of the test sample.

Standards of the cylinder and plunger that are used in theabove-mentioned measuring method are as follows:

Plunger

Weight: 190 g

Outer diameter: 21.80 ± 0.05 mm

Total height: 115.0 mm

Material: iron (having a hollow structure)

Cylinder

Inner diameter: 22.00 ± 0.05 mm

Height: 100.0 mm (from the bottom of the cylinder)

In addition to the above-mentioned excellent water dispersibility, thebuilder of this invention has such a specific characteristic that notonly before exchange of calcium ion but also after exchange of calciumion the surface potential of the builder dispersed in water is uniformlykept negative. As pointed out hereinbefore, clothes and other fibrousarticles in the washing liquid are negatively charged, and therefore,when fine particles of the builder are uniformly charged negatively atthe washing and rinsing steps, adhesion of the builder particles toclothes and the like is remarkably controlled, and a good rinsing statecan be attained and troubles such as powder falling can be effectivelyprevented. When the measurement is carried out according to the methoddescribed below, it is seen that the builder of this invention isremarkably excellent over known zeolites with respect to the property ofretaining the negative charge after exchange of calcium ion, andtherefore, it is apparent that the builder of this invention isexcellent over known zeolites with respect to the rinsing property andprevention of such troubles as powder falling.

The surface charge characteristic of the alkali aluminosilicate can bedetermined according to the following measurement method.

(xi) Method for electrophoretic determination of adhesion of zeoliteparticles to

anode after exchange of calcium ion:

A box-type vessel composed of a methyl methacrylate resin (innerdimensions = 31 mm × 85 mm × 129 mm) is charged with 200 ml of deionizedwater. A zeolite sample is dried, pulverized and passed through a sieveof 200 Tyler mesh, and the resulting powdery zeolite is dried for 2hours in a drier maintained at 110° C. to form a test sample. In theabove-mentioned deionized water is suspended 0.2 g of the so formed testsample. Two platinum plates (each having a size of 0.25 mm × 80 mm × 100mm) are set as electrodes in the box-type vessel with a clearance of30.5 cm therebetween so that the platinum plates are contacted with boththe side faces of the box-type vessel, respectively. A direct currentvoltage is applied between the two electrodes to flow an electriccurrent of 0.1 A for 10 minutes. After completion of application ofelectricity, the states of adhesion of powder particles to the anode andcathode surfaces are examined with the naked eye and evaluated accordingto the following scale:

5: the powder adheres to the entire surface of the anode but does notadhere to the surface of the cathode at all.

4: the powder adheres partially to the surface of the anode but ithardly adheres to the surface of the cathode.

3: the powder hardly adheres to the surface of the anode or the surfaceof the cathode.

2: the powder hardly adheres to the surface of the anode but adherespartially to the surface of the cathode.

1: the powder does not adhere to the surface of the anode but it adheresto the entire surface of the cathode.

ACID TREATMENT OF SMECTITE CLAY MINERAL

In the preparation of the zeolite builder of this invention, a smectiteclay mineral is first subjected to the acid treatment under suchconditions that at least the X-ray diffraction peak of the plane index[001] substantially disappears, to thereby form activated silica oractivated alumina-silica.

In this invention, as the smectite clay mineral, there can be used, forexample, so called montmorillonite clay minerals such as acid clay,bentonite, subbentonite and Fuller's earth, and beidellite, saponite andnontronite. These clay minerals may be used singly or in the form of amixture of two or more of them. Further, these clay minerals may be usedin the form of mixtures with other type clay minerals. Moreover,naturally modified smectite clay minerals, for example, a clay having aslightly destroyed smectite multi-layer structure, which is produced atSanko, Shibata city, Niigata prefecture, Japan, may also be used in thisinvention.

In general, a smectite clay mineral has as the basic structure athree-layer structure comprising a central octahedral layer sandwichedbetween two tetrahedral layers of SiO₂, and a great number of thesebasic three-layer structures are laminated in the direction of the axisC to form a multi-layer crystal structure inherent of the smectite claymineral. The acid treatment is carried out under such conditions thatthis multi-layer crystal structure is substantially destroyed; namelythe X-ray diffraction peak of the plane index [001] substantiallydisappears. By this acid treatment, it is made possible to obtain azeolite having a high calcium binding property and a very fine primaryparticle size.

FIG. 8 illustrates an X-ray diffraction pattern of acid clay produced atNakajo, Niigata prefecture, Japan, and FIG. 9 illustrates an X-raydiffraction pattern of alumina-silica treated under conditions 1-2 ofExample 5 given hereinafter, in which destruction of the multi-layercrystal structure by the acid treatment is insufficient. FIGS. 10 and 11illustrate X-ray diffraction patterns of alumina-silica obtained inExample 5 hereinafter, in which the multi-layer crystal structure iscompletely destroyed by the acid treatment. In samples shown in FIGS. 8and 9, the X-ray diffraction peak of the plane index [001] is clearlyleft, but in samples shown in FIGS. 10 and 11, the X-ray diffractionpeak of the plane index [001] substantially disappears.

From results obtained in Example 5 given hereinafter, it will readily beunderstood that destruction of the multi-layer crystal structure isimportant for obtaining a zeolite having an excellent calcium bindingproperty and a very fine primary particle size. For example, if there isemployed acid clay per se having an X-ray diffraction pattern shown inFIG. 8 or aluminosilica in which destruction of the multi-layer crystalstructure is insufficient, such as sample 5-2 shown in FIG. 9 and Table12 given hereinafter, crystallization to a zeolitic structure isinsufficient and properties of the builder, such as the calcium bindingproperty, are degraded. Further, in such case, the primary particle sizeis larger than 1 μ and the intended objects of this invention cannot beattained. In contrast, when alumina-silica having X-ray diffractionpatterns as shown in FIGS. 10 and 11, which have been acid-treatedaccording to this invention, higher crystallization to a zeoliticstructure can be attained under the same zeolite-forming conditions andexcellent builder characteristics can be obtained. Moreover, a builderhaving a very fine primary particle size can be obtained.

In this invention, in order to obtain a zeolite builder having a veryfine primary particle size and preferred characteristics, it isdesirable for the activated silica or alumina-silica obtained by theacid treatment to have a degree of the crystal destruction (D.C.) lowerthan 15%, especially lower than 5%, as measured according to the methoddescribed below, with respect to the peak of the plane index [001].

(xii) Method for determination of degree of crystal destruction (D.C.):

X-ray diffraction patterns of the starting raw clay mineral andacid-treated clay mineral are obtained according to the method fordetermining X-ray diffraction patterns, which has been described in (i)above.

With respect to each of the X-ray diffraction patterns of the startingand acid-treated clays, the height of the peak of the plane index [001](when the measurement is carried out under conditions specified in thisinvention, the peak of the plane index [001] appears at 4° to 7°, whichdiffers to some extent depending on the kind of the clay) and the heightof the peak of the plane indexes [110] and [020] (when the measurementis carried out under conditions specified in this invention, a singlepeak of the plane indexes [110] and [020] appears at 19.6° to 19.9°) aremeasured, and [001] D.C. and [020] D.C. values (%) are calculatedaccording to the formula given below and the degree of crystaldestruction by the acid treatment is evaluated based on these values.##EQU3##

In this invention, in order to obtain a zeolite builder having a finestprimary particle size and being most excellent in buildercharacteristics, it is preferred that the acid treatment be carried outunder such conditions that the value of [020] D.C. is lower than 15%,especially lower than 5%; namely even the basic three-layer structure ofthe starting clay is substantially destroyed.

The acid treatment of the smectite clay mineral can be performed byknown methods, so far as the above-mentioned requirement is satisfied.As the acid, there can be used, for example, mineral acids such assulfuric acid, hydrochloric acid and nitric acid, and organic acids suchas benzene-sulfonic acid, toluene-sulfonic acid and acetic acid.However, a mineral acid such as sulfuric acid is ordinarily used. Thecontact of the clay with the acid may be performed according to knownmethods, and methods for the acid treatment of clays, which werepreviously proposed by us, can be effectively and preferably adopted(see Japanese Patent Publications Nos. 5666/53, 112/54, 2169/54,2960/57, 11208/70, 11209/70, 44154/72, etc.). For example, the so-calledslurry activation method in which a clay is contacted with an acid inthe slurry state, the so-called granule activation method in which agranulated clay is subjected to solid-liquid contact with an acid andthe so-called dry activation method in which a mixture of a clay and anacid is reacted in the dry state (in the granulated form) and then, theresulting salts are extracted may be adopted for accomplishing the acidtreatment of this invention.

The concentration of the acid used for the acid treatment, the treatmenttemperature and the treatment time are changed depending on the kind ofthe clay mineral and the treatment method, and it is difficult tospecify these conditions. For example, when the acid treatment isperformed according to the dry method, a smectite clay mineral such asmentioned above is intimately contacted with 0.3 to 1.5 equivalents,especially 0.5 to 1.2 equivalents, based on the basic component in theclay, of an acid as it is or in the form of an aqueous solution in sucha proportion that the amount of the acid or its aqueous solution is 0.5to 1.2 parts by weight per part by weight of the clay on the dry basis,to thereby form directly a plastic or solid reaction product and thisreaction product is treated in an aqueous medium at a pH lower than 1 toremove the basic metal component in the reaction product by extraction.The basic metal component referred to includes all the basic componentscontained in the clay, such as alkali metal, alkaline earth metal, ironand aluminum components. When the mixing ratio of the clay and the acidor its aqueous solution is maintained in the above-mentioned range, asolid or creamy admixture is formed. This admixture is maintained at 60°to 300° C. for 10 to 600 minutes under such conditions that the X-raydiffraction peak of the plane index [001] substantially disappears,whereby the reaction is completed. Then, soluble basic components in thereaction product are extracted and removed by treating the reactionmixture in an aqueous medium having a pH lower than 1, preferably a pHlower than 0.5. In order to prevent hydrolysis of the soluble basiccomponents, it is important that the removal and extraction of the basiccomponents should be performed under the above-mentioned pH conditions.If colloidal iron components formed by hydrolysis are included in theresulting activated alumina-silica, there is often observed a tendencythat the yield of the resulting synthetic zeolite or the degree ofcrystallization is considerably reduced.

When activated alumina-silica is prepared by the acid treatment bysolid-liquid contact of a granulated clay and a mineral acid, themineral acid having a concentration of 10 to 98% is added to the clay inan amount of 0.01 to 0.1 part by weight per part by weight of the clayon the dry basis and the mixture is granulated to form a granularproduct which will not be disintegrated under conditions of thesubsequent acid treatment. This non-disintegratable granulated clay isimmersed in an aqueous solution of a mineral acid having a concentrationof 5 to 72%, especially 10 to 50%, at a temperature in the range of fromroom temperature to the boiling point of the acid solution for 0.5 to100 hours so that the X-ray diffraction peak of the plane index [001]substantially disappears in the clay.

The acid treatment of the clay mineral can also be accomplishedaccording to the wet method in which the clay is dispersed in a mineralacid such as sulfuric acid having a concentration of 5 to 98% and theclay is treated in the slurry state. In this case, the acid treatmentconditions may be the same as those adopted in the above-mentioned acidtreatment for the granulated clay.

In this invention, activated silica or activated alumina-silica is thusformed according to the degree of the acid treatment. This product hasmuch higher activities, especially a much higher surface activity, thanthe untreated clay mineral or a product acid-treated under conditionsoutside the range specified in this invention. More specifically, theactivated alumina-silica intermediate that is used in this invention hasan aromatic adsorption index (AAI) of at least 16, especially 20 to 60,as measured according to the method described below. In view of the factthat untreated clay minerals have, in general, an AAI value lower than15, it will readily be understood that the activated silica oralumina-silica formed by the above-mentioned acid treatment has aremarkably high surface activity. It is believed that because of thishigh surface activity, a synthetic zeolite for a detergent builder whichhas a very fine primary particle size and an excellent crystallinity canbe obtained from this intermediate according to this invention.

(xiii) Method for determination of AAI values:

A sample which has been appropriately pulverized in a mortar in advanceis charged in a plugged weighing bottle having a suitable capacity, andthe bottle is allowed to stand still for 3 hours in a drier maintainedat 150° ± 5° C. and then placed in a desiccator. The content is thuscooled to room temperature naturally to form a test sample.

In a clean test tube for a centrifuge is charged 1 ± 0.005 g of the testsample, and 2 ± 0.05 cc of a liquid mixture comprising 30 parts byvolume of dehydrated toluene and 70 parts by volume of dehydratedisooctane is added to the test sample by using a microburet. Then, thetest tube is plugged and is shaken with a shaking angle of about 60°from the vertical line while the head of the tube is being lightlypressed, to thereby disperse the sample sufficiently in the liquid.

A rubber cap is set on the head portion of the test tube so as toprevent falling-out of the plug of the tube, and the test tube isattached to a shaking machine and shaken at a rate of 100 reciprocationsper minute. Then, the test tube is subjected to an action of acentrifuge to form a supernatant. Refractive indexes of the obtainedsupernatant and the starting liquid mixture are measured by Abbe'srefractometer, and the AAI value (the aromatic adsorption index) iscalculated according to the following formula: ##EQU4## wherein ##EQU5##denotes the refractive index of the liquid mixture comprising 30 partsby volume of toluene and 70 parts by volume of isooctane, and ##EQU6##represents the refractive index of the supernatant.

ALKALI PRE-TREATMENT

One of important features of this invention resides in the novel findingthat when the activated silica or activated aluminosilica obtained bythe acid treatment of a smectite clay mineral such as mentioned above istreated with an alkali hydroxide or a water-soluble alkali metalsilicate prior to the synthesis of the intended zeolite to form analkali metal polysilicate or alkali metal polyaluminosilicate having acomposition in which the Na₂ O/SiO₂ molar ratio is in the range of from1/3.5 to 1/500, preferably from 1/4 to 1/400, especially preferably from1/7 to 1/300, a zeolite having an extremely fine particle size and beingexcellent in various builder characteristics can be obtained.

More specifically, as in case of sample H-3 shown in Example 2 givenhereinafter, if activated silica obtained by the acid treatment of asmectite clay mineral is directly mixed with aluminum and alkali metalcomponents and water and the mixture is subjected tozeolite-crystallizing-out reaction, the resulting zeolite has a primaryparticle size larger than 1 μ and is still insufficient in the waterdispersibility and rinsing property. Further, as in case of sample H-4shown in Example 2, if an alkali hydroxide is added to activated silicaobtained by the acid treatment of a smectite clay mineral so that acomposition substantially same as the composition of commerciallyavailable water glass can be attained and additional amounts of aluminumand alkali metal components and water are added to the resultingreaction product to effect zeolite-crystallizing-out reaction, theresulting zeolite has a primary particle size considerably larger than 1μ and a builder excellent in such properties as the water dispersibilityand rinsing property cannot be obtained at all. In contrast, to ourgreat surprise, if an alkali metal hydroxide or water-soluble alkalimetal silicate is added to an acid-treated clay so that the Na₂ O/SiO₂molar ratio is within the above-mentioned range and the pre-treatment(preliminary aging treatment) is conducted, a finely divided zeolitehaving a primary particle size smaller than 1 μ can be exceptionallyobtained. This fact will be apparent from results obtained in respectiveExamples given hereinafter.

The reason why a finely divided zeolite having a primary particle sizesmaller than 1 μ can be obtained by the specific combination of the acidtreatment of a smectite clay mineral and the alkali pre-treatment inthis invention has not been completely elucidated. However, it isconstrued that for formation of such fine zeolite there must be presenta great number of crystal nuclei in the zeolite-crystallizing-outreaction system or the nucleus-forming speed should be very high whilethe crystal-forming speed is low and if an intermediate formed byacid-treating a smectite clay mineral and treating the acid-treated claywith an alkali is used as a raw material for synthesis of a zeolite,such requirement is effectively satisfied. In this invention, themulti-layer crystal structure of a smectite clay mineral, preferablytogether with the basic three-layer structure, is destroyed by the acidtreatment, and it is believed that by the subsequent alkalipre-treatment the tetrahedral layer composed of SiO₄ is combined withthe alkali and this provides promptly a great number of crystal nucleiat the zeolite-crystallizing-out rection. If the acid-treated clay isdirectly subjected to the zeolite-forming reaction without the alkalipretreatment, the speed of formation of nuclei is very low and resultingzeolite particles are coarsened. It is construed that when water-solublesodium silicate is directly employed as the starting material for thesynthesis of a zeolite or when the acid-treated clay is pre-treated withan alkali in an amount more than the amount specified in this invention,since the silica component is dissolved in an aqueous solution in theform of a monomer or oligomer, the nucleus-forming speed is relativelylow and hence, the resulting zeolite particles are coarsened.

The pre-treatment of the acid-treated clay with an alkali metalhydroxide or a water-soluble alkali metal silicate may be accomplishedby optional methods, so far as the above-mentioned Na₂ O/SiO₂ molarratio requirement is satisfied and both the components are intimatelycontacted with each other. In general, in order to attain an intimatecontact between both the components, it is preferred that both thecomponents be contacted in the presence of water in an amount of 1 to 49parts by weight, especially 2 to 19 parts by weight, per part by weightof the acid-treated clay. This water may be incorporated into either theacid-treated clay or the alkali metal hydroxide or water-soluble alkalimetal silicate or in both of them. In general, it is preferred that anaqueous slurry of the acid-treated clay be mixed with an aqueoussolution of the alkali metal hydroxide or water-soluble alkali metalsilicate.

Since the acid-treated clay per se has a high activity, good results areobtained even when the pretreatment is carried out at room temperature,but if desired, the temperature may be elevated to about 70° C. Apreferred pre-treatment temperature is in the range of from roomtemperature to the boiling point of the mixture, especially from 20° to95° C. The time for aging the mixture of both the components is changeddepending on the temperature, but in general, the pretreatment iscarried out for 0.2 to 100 hours, especially 2 to 50 hours.

The pre-treatment may be performed under atmospheric pressure, but ifdesired, the pre-treatment can be conducted under heating at a pressureof up to about 5 atmospheres (gauge) in an autoclave or other sealedvessel. It also is possible to perform the pre-treatment in a dryingatmosphere. In this case, the pre-treatment can be completed whiledrying the mixture of the acid-treated clay and alkali component. Whenthe mixture of the acid-treated clay and alkali component is in a pastyor plastic state, the mixture may be molded into granules, and thegranules may be steamed in a water vapor atmosphere and dried or heated,whereby the intended pre-treatment is accomplished.

ADJUSTMENT OF PARTICLE SIZE

In order to obtain a finely divided zeolite in this invention, it ispreferred that the particle size of the alkali metal polysilicate oralkali metal polyaluminosilicate to be used for thezeolite-crystallizing-out reaction be adjusted so that particles havinga size smaller than 5 μ occupy at least 20% by weight, especially 50% byweight, of the total particles and particles having a size larger than20 μ occupy less than 30% by weight, especially less than 10% by weight,of the total particles.

This particle size adjustment may be performed before the acidtreatment, during the acid treatment, after the acid treatment (beforethe alkali treatment), during the alkali treatment or after the alkalitreatment. If desired, it is possible to perform this particle sizeadjustment in two or more stages, for example, during the acid treatmentand during the alkali treatment. For example, when the starting clay tobe subjected to the acid treatment is subjected to one or more of dryand wet pulverizing operations and classifying operations using ahydrualic elutriation, an air elutriation, a liquid cyclone, a fluidizedbed and the like, the particle size of the raw material for the alkalimetal polysilicate or polyaluminosilicate can be accomplished. When theparticle size adjustment is thus made on the starting clay, impuritiessuch as stone and sand contained in the raw clay mineral are effectivelyremoved and a silica or aluminosilica intermediate having an enhancedreactivity can be obtained. Therefore, in this invention, there isadvantageously adopted, for example, a method in which a fluidizing gasis blown into an as-produced starting smectite clay mineral underagitation to separate the raw material into an upper fluidized layer offine clay particles and a lower fixed or slightly fluidized layer ofcoarse particles containing stone, sand and other impurities.

Further, an alkali metal polysilicate or alkali metalpolyaluminosilicate intermediate for the synthesis of a finely dividedzeolite, which has the above-mentioned particle size distribution, canbe obtained by wet-pulverizing an acid-treated clay (acid-washed clay)or an alkali-treated product in a pulverizer such as a ball mill, a tubemill, a mixer, an attritor, a shaking mill or the like and if necessary,classifying the resulting particles by a liquid cyclone or the like.

Of course, it is possible to perform the particle size adjustmentsimultaneously with the acid treatment or the alkali treatment. In thiscase, a slurry of the starting clay and an acid or a slurry of theacid-treated clay and an alkali is preferably treated in a pulverizersuch as a ball mill or a mixer or a highly shearing agitator. The slurryis passed through a classifying machine such as a liquid cyclone duringthe acid or alkali treatment or after the acid or alkali treatment tocollect particles having a desirable size. By any of the foregoingparticle size adjustment treatments, an intermediate having theabove-mentioned desirable particle size distribution can be obtained.

If necessary, such treatments as water washing and drying may beperformed before or after the acid treatment, the alkali treatment andthe particle size adjustment. The alkali metal polysilicate orpolyaluminosilicate intermediate, which has been subjected to theabove-mentioned treatments, is used for the synthesis of the intendedzeolite in an optional form, for example, a dry powder, a cake or aslurry.

PREPARATION OF HOMOGENEOUS MIXTURE

According to the process of this invention, the above-mentioned finelydivided alkali metal polysilicate or polyaluminosilicate is mixed withadditional amounts of alumina and alkali metal components and water andthe mixture is aged to form a homogeneous admixture having a compositioncapable of forming zeolite of the type A.

As the alumina component, there can be used, for example, fine powdersof amorphous alumina such as hydrogel and xerogel of aluminum hydroxide,alumina monohydrate such as boehmite and pseudo-boehmite, aluminatrihydrate such as bayerite, gibbsite and nordstrandite, and activealumina such as γ-alumina, η-alumina, δ-alumina, κ-alumina, θ-alumina,χ-alumina and -alumina. As the alkali metal component, there can bepreferably employed alkali metal hydroxides such as sodium hydroxide,potassium hydroxide and lithium hydroxide. The alumina and alkali metalcomponents may be used in the form of a compound or mixture of both thecomponents. Use of an alkali metal aluminate is especially preferred.When an alkali metal aluminate is employed, if an excessive amount ofthe alumina or alkali metal components is necessary, such component isfed to the reaction system in the form incorporated into the alkalimetal aluminate.

In this invention, the alkali metal polysilicate or alkali metalpolyaluminosilicate is mixed with additional amounts of alumina andalkali metal components and water at known mixing ratios. In knownprocesses for production of zeolite of the type A, zeolite-formingcomponents are used at the following ratios (based on the oxides):

    ______________________________________                                                Ordinary Range                                                                             Preferred Range                                          ______________________________________                                        SiO.sub.2 /Al.sub.2 O.sub.3                                                             0.06 - 5       0.1 - 3.5                                            Na.sub.2 O/SiO.sub.2                                                                    0.3 - 18       0.5 - 5                                              H.sub.2 O/Na.sub.2 O                                                                     4 - 300       15 - 150                                             ______________________________________                                    

In this invention, the foregoing components are mixed together so thatthe above mixing ratios are attained.

However, in this invention, in order to prepare a synthetic zeolitehaving a fine particle size and being excellent in builder effects froman alkali metal polysilicate or alkali metal polyaluminosilicateintermediate derived from a smectite clay mineral, it is preferred thatattention be paid to the following points.

It is first of all preferred to avoid direct addition of an alkali metalhydroxide to the alkali metal polysilicate or alkali metalpolyaluminosilicate in such an amount as will solubilize saidintermediate. When this intermediate is directly mixed with a largeamount of an alkali metal hydroxide, a zeolite having a coarse particlesize tends to crystallize out, and this tendency is especiallyconspicuous when a water-soluble alkali metal silicate is used as thesilica component. Accordingly, it is most preferred that an alkalineaqueous solution of an alkali metal aluminate be gradually added to anaqueous dispersion of the alkali metal polysilicate or alkali metalpolyaluminosilicate. Of course, an aqueous dispersion of the alkalimetal polysilicate or alkali metal polyaluminosilicate and a solution ofan alkali metal aluminate may be added continuously or intermittentlyinto water simultaneously or alternately.

In this invention, since a solid silicate or aluminosilicateintermediate is used for the synthesis of zeolite, at the step of mixingzeolite-forming components there is an optimum alkali concentration forobtaining a zeolite having a high degree of crystallization and a fineparticle size, and it generally is preferred that an alkaliconcentration (CA, mole %) defined by the following formula be in therange of from 7 to 0.25 mole %, especially from 5 to 0.5 mole %:##EQU7## wherein [SiO₂ ], [Al₂ O₃ ], [Na₂ O] and [H₂ O] represent molenumbers of SiO₂, Al₂ O₃, Na₂ O and H₂ O, respectively, in the mixture.

Moreover, in order to prepare a zeolite having a high degree ofcrystallization and a fine particle size while controlling formation ofsodalite hydrate effectively, it is preferred that at the step of mixingthe zeolite-forming components the alkali concentration be adjusted soas to satisfy requirements expressed by the following empirical formulaedepending on the temperature and time for crystallizing out zeolite:##EQU8## wherein t stands for the crystallizing-out time (hr), T standsfor the crystallizing-out temperature (° K., absolute temperature), andCA stands for an alkali concentration (mole %) in the zeolite-forminghomogeneous mixture.

When the above alkali concentration is higher than 7 mole %, thetendency of crystallization of sodalite hydrate is enhanced as comparedwith the case where the alkali concentration is in the above-mentionedrange, though this tendency differs to some extent depending on thetemperature or time for mixing the zeolite-forming components asdescribed hereinafter. A sodalite hydrate-containing zeolite is inferiorin the calcium binding property and the washing power is low when it isused for a detergent builder. When the alkali concentration is lowerthan the above range, the resulting zeolite tends to have coarserparticles, and the rate of the reaction tends to decrease considerably.

Another point that must be taken into consideration at the step ofmixing zeolite-forming components is that incorporation of colloidaliron compounds such as colloidal iron hydroxide into the reactionmixture must be avoided as much as possible. In general, industriallyavailable alkali metal aluminates contain about 100 to about 5000 ppm,based on the oxide of colloidal iron. We have found that if acommercially available alkali metal aluminate is used for the synthesisof zeolite as it is, a long time is required for crystallization andsodalite hydrate is formed, resulting in reduction of the calciumbinding property, and that the resulting zeolite is colored reddishbrown beyond an allowable limit. It has been found that this defect caneasily be overcome by simple means. More specifically, if suchcommercially available alkali metal aluminate is diluted with water sothat the concentration as Al₂ O₃ is 3 to 20% by weight, cohesion iscaused in the coloidal iron compounds to form flocs and if the so formedflocs are separated by filtration, the concentration of colloidal ironcan be reduced to a level lower than 50 ppm as Fe₂ O₃.

When a commercially available sodium silicate solution is mixed with acommercially available sodium aluminate solution, since the respectivecomponents are gelled and highly viscous, a heterogeneous gel is readilyformed. In contrast, in this invention, by using the above-mentionedspecific zeolite-forming materials and adopting the above-mentionedspecific mixing method, an entirely homogeneous slurry can easily beobtained without such difficulty. This slurry may be aged underagitation, if desired. The aging temperature and time are notparticularly critical, but in general, it is preferred that the aging becarried out at 0° to 50° C., especially 10° to 30° C., for 0.1 to 100hours, especially 1 to 20 hours.

CRYSTALLIZING-OUT OF SYNTHETIC ZEOLITE

According to the process of this invention, the above-mentionedhomogeneous admixture having a specific composition is heated tocrystallize out a finely divided zeolite having a primary particle sizesmaller than 1 μ .

Crystallizing-out of a crystalline alkali metal aluminosilicate can beaccomplished under known conditions, but in general, it is preferred tocrystallize out zeolite particles from a slurry at a temperature of 60°to 200° C., especially 70° to 100° C., over a period of 0.1 to 500hours, especially 0.5 to 50 hours. Of course, it is possible to conductcrystallizing-out of zeolite particles under a pressure generated by thereaction or under pressurization with an inert gas by using an autoclaveor other pressure vessel. In this invention, however, adoption of suchconditions is not necessary at all, but zeolite particles can becrystallized out under mild conditions.

Agitation conditions are not particularly critical at the step ofcrystallizing out zeolite, but an ordinary crystallizing tank equippedwith an ordinary agitator can be used conveniently in this invention.

In order to obtain a synthetic zeolite especially valuable as adetergent builder, it is preferred that zeolite be crystallized outunder such alkali concentration, temperature and time conditions as willsatisfy requirements represented by the following empirical formulae:##EQU9## wherein t stands for the crystallizing-out time (hr), T standsfor the crystallizing-out temperature (° K., absolute temperature), andCA stands for an alkali concentration (mole %) in the zeolite-forminghomogeneous mixture.

If the above requirements are satisfied at the crystallizing-out step,formation of sodalite, which is often observed in preparing zeolitesfrom clay minerals, can be effectively controlled.

The so formed zeolite composed of very fine particles can be used as asynthetic zeolite product as a detergent builder as it is in theas-prepared slurry form or after it has been subjected to a knownsolid-liquid separation operation such as filtration or centrifugalseparation and to water washing and drying.

The crystallized-out synthetic zeolite is separated from the motherliquor in the state where it contains at least a part of the excessivealkali included in the mother liquor, and an acid or acidic salt isadded to the so separated composition and the alkali is neutralizedunder such a condition that the pH of the composition is higher than9.0, whereby the buffer capacity (S) of the zeolite can be remarkablyimproved. As such acid or acidic salt, there can be employed thosehaving a pKa value of at least 2, especially at least 2.5, for example,phosphorus oxy acids such as phosphoric acid, phosphorous acid andmetaphosphoric acid, acidic salts of these phosphorus oxy acids,inorganic acids such as carbonic acid, boric acid, monosodium borate andactivated silicic acid solutions, organic acids such as citric acid,oxalic acid, tartaric acid, succinic acid, maleic acid, malonic acid,gluconic acid, itaconic acid, thioglycolic acid,ethylenediamine-tetraacetic acid, nitrilotriacetic acid, diglycolicacid, sulfoitaconic acid, trimesic acid, pyromellitic acid, polyacrylicacid, maleic anhydride-methyl vinyl ether copolymers and CMC, and acidicsalts of these inorganic and organic acids.

When phosphoric acid or its acidic salt is used for neutralizing theexcessive alkali, by heating the resulting phosphate-containing zeoliteat an elevated temperature, for example, 300° C. or higher, thephosphate may be converted to a condensed phosphoric acid salt, forexample, a pyrophosphate.

USE

The synthetic zeolite for a detergent builder according to thisinvention can be combined with various surface active agents and be usedas detergent compositions. As such surface active agent, there can bementioned, for example, anionic surface active agents such as sodiumsalts of fatty acids, sodium salts of higher alcohol-sulfuric acidesters, sodium alkyl benzenesulfonates, sodium salts of alkyl sulfates,alkylolamide sulfuric acid esters, α-olefin sulfonate sodium alkylsulfonates, sodium alkyl naphthalene-sulfonates, sulfonated fatty acidesters, sulfonated heterocyclic compounds, sulfonated fatty acid amidessodium dialkyl sulfosuccinates, fatty acid-amino acid condensates andTurkey red oil, non-ionic surface active agents such as polyoxyethylenealkyl ethers, polyoxyethylene alkyl aryl ethers, polyethylene glycolfatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylenefatty acid amide esters, polyhydric alcohol fatty acid esters,polyoxyethylene polyhydric alcohol fatty acid esters and alkylol amides,and amphoteric surface active agents such as betaine type surface activeagents, imidazoline type surface active agents, sulfonic acid typeamphoteric surface active agents and alanine type amphoteric surfaceactive agents. These surface active agents may be used singly or in theform of mixtures of two or more of them.

The so formed detergent compositions may further comprise one or more ofother inorganic and organic builders according to the intended use. Asthe inorganic builder, there can be mentioned, for example, polysilicatebuilders, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate,sodium orthophosphate, sodium pyrophosphate, potassium pyrophosphate,sodium tripolyphosphate, sodium tetraphosphate, sodiumhexamethaphosphate, borax, sodium chloride and sodium borate. As theorganic builder, there can be mentioned, for example, sodium citrate,sodium oxalate, CMC, sodium nitrilotriacetate, sodium diglycolate,sodium gluconate, sodium hydroxysuccinate, sodium mellitate, sodiumethylenediaminetetraacetate, sodium polymaleate, sodium polyitaconate,sodium polymesaconate, sodium polyfumarate, sodium polyaconitate, sodiumpolycitraconate, sodium polymethylene-malonate, sodiumcarboxymethoxymalonate, sodium carboxymethoxysuccinate, sodiumcis-cyclohexanehaxacarboxylate, sodium cis-cyclopentane-tetracarboxylateand sodium phloroglucinol-trisulfonate.

These detergent composition may further comprise known additivescustomarily used in this field, for example, bubble-controlling agents,fluorescent whitening agents, bluing agents, other colorants, perfumesand caking preventing agents.

The synthetic zeolite of this invention is incorporated in a detergentcomposition in an amount of 0.1 to 95 % by weight, especially 1 to 50 %by weight, based on solids, though this amount is changed to some extentdepending on the intended use of the detergent.

By virtue of the above-mentioned various characteristic properties, thesynthetic zeolite builder of this invention can be used effectively forpowdery and granular detergents, especially household powdery andgranular detergents. Further, it must be noted that the foregoingvarious advantages of the synthetic zeolite of this invention cansimilarly be attained when they are used for various dry-cleaningdetergents, liquid detergents, solid soaps, powdery soaps, washingpowders, detergents for table wares, detergents for glass and tiles anddetergents for automobiles.

This invention will now be described in detail by reference to thefollowing Examples and Comparative Examples that by no means limit thescope of this invention.

EXAMPLE 1

This Example illustrates the preparation of a synthetic zeolite fordetergent builders from acid clay produced in Nakajo, NiigataPrefecture, Japan, as the smectite clay mineral.

The acid clay produced in Nakajo, Niigata Prefecture, Japan, which wasused in this Example, contained 45 % by weight in the as-produced state,and the metallic oxide composition of the clay (based on the productdried at 110° C.) was as follows:

    ______________________________________                                        SiO.sub.2          72.1% by weight                                            Al.sub.2 O.sub.3   14.2% by weight                                            Fe.sub.2 O.sub.3    3.87% by weight                                           MgO                 3.25% by weight                                           CaO                 1.06% by weight                                           Ignition loss       3.15% by weight                                           ______________________________________                                    

The starting acid clay was molded into columns having a diameter of 5 mmand a length of 5 to 20 mm, and 1250 Kg (as the dried product) of themolded clay was charged in a lead-lined wood tank having a capacity of 5m³ and 3300 l of sulfuric acid having a concentration of 47 % by weightwas added thereto. Then, the temperature was elevated to 90° C. and theacid treatment of the clay granules was carried out for 40 hours.Sulfates of basic components which had reacted with sulfuric acid wereremoved by decantation using a dilute solution of sulfuric acid andwater, and the water washing was conducted until no sulfate ion wasdetected. Thus, a granular acid-treated product was obtained.

The degree of destruction of the crystal structure of the above granularacid-treated product was determined from the X-ray diffraction peaks.The granular acid-treated product was dried for 2 hours in a driermaintained at 110° C. and the dried product was analyzed. Obtainedresults are shown in Table 1. This acid-treated product will hereinafterbe referred to as "activated silica" (having a water content of 50% byweight) (sample 1-1).

                  Table 1                                                         ______________________________________                                        Acid-Treated Product                                                                            Sample 1-1                                                  ______________________________________                                        Composition (% by weight)                                                     Ignition loss       3.71                                                      SiO.sub.2           94.26                                                     Al.sub.2 O.sub.3    1.27                                                      Fe.sub.2 O.sub.3    0.39                                                      MgO                 0.30                                                      CaO                 0.07                                                      SiO.sub.2 /Al.sub.2 O.sub.3 Mole Ratio                                                            126.2                                                     AAI                 38                                                        [001] DC (%)        undetectable                                              [020] DC (%)        2                                                         ______________________________________                                    

The above activated silica was wet-pulverized in a ball mill whileadding water to adjust the concentration to 20% by weight, to obtain anactivated silica slurry (sample 1-2) having a particle size distributionshown in Table 2 (as measured by particle size measurement device ModelPSA-2 -manufactured by Hitachi Seisakusho K. K.).

                  Table 2                                                         ______________________________________                                        Particle Size Distribution                                                                      Sample 1-2                                                  ______________________________________                                        smaller than 5 μ 46.0%                                                     5 to 20 μ        54.0%                                                     larger than 20 μ 0%                                                        ______________________________________                                    

A stainless steel vessel having a capacity of 2 m³ was charged with 79.6Kg of the slurry (sample 1-2) and 46.6 Kg of a commercially availablecaustic soda solution (containing 49 % of NaOH) was added thereto. Themixture was agitated at 60° C., for 6 hours to obtain an alkali metalpolysilicate A having a composition corresponding to Na₂ o·8.8SiO₂.

For comparison, in the same manner as described above, the samecommercially available caustic soda solution was added to the aboveslurry (sample 1-2) at 20° C. to obtain an alkali metal polysilicateslurry B having a composition corresponding to Na₂ o·8.8SiO₂, and theslurry was immediately used for the preparation of a synthetic zeolitewithout aging.

As one of conditions for the preparation of a synthetic zeolite fordetergent builders, the following composition (oxide mole ratios) waschosen.

Na₂ O/SiO₂ = 0.9

SiO₂ /Al₂ O₃ = 2.0

H₂ O/Na₂ O = 50.0

CA = 1.9 %

An alkali metal aluminate solution having a composition of 18.54% of Na₂O, 19.1% of Al₂ O₃ and 62.4 % of H₂ O and an Na₂ O/Al₂ O₃ molar ratio of1.6/1 was prepared by dissolving commercially available aluminumhydroxide to commercially available caustic soda. This aluminatesolution was formed as the alkali metal aluminate solution to be addedto the above alkali metal polysilicate A or B so as to attain the abovecomposition (oxide mole ratios).

Process for preparation of synthetic zeolite for detergent builders

Water was added to the alkali metal polysilicate slurry A or B to adjustthe SiO₂ concentration to 10 %, and the mixture was charged in astainless steel vessel having a capacity of 3.5 m³. A solution formed byadding water to the above alkali metal aluminate solution underagitation at 20° C. to adjust Na₂ O and Al₂ O₃ concentrations to 12.5%and 12.8%, respectively, was added to the above mixture over a period ofabout 80 minutes. The mixture was once gelled and it was finallyconverted to a homogeneous slurry. Then, the mixture was heated at 95°C. and reaction was carried out for 3 hours under agitation to formcrystalline particles of a zeolite. Then, the reaction product waswashed with water and filtered. The filter cake was recovered and driedin a drier maintained at 110° C. to obtain a synthetic zeolite (sample1-3 or sample H-1).

The so prepared zeolite sample 1-3 (derived from the alkali metalpolysilicate slurry A) and zeolite sample H-1 (derived from the alkalimetal polysilicate slurry B) were subjected to various tests accordingto the test methods described hereinbefore to determine the X-raydiffraction crystal form, the crystallization degree (CR), the calciumion binding property (CI), the initial buffer capacity (R), the buffercapacity (S), the effective alkali quantity (Qc), the suspension pH, theoil absorption (OA), the bulk density (BD), the primary particle size(Dp), the secondary particle size distribution (Ds), the sedimentationspeed (Vs), the Methylene Blue Adsorbing Property (AM) and the surfacecharge controlling property (ED). Obtained results are shown in Table 3.

In addition to the sample H-1 were prepared by using the non-aged alkalimetal polysilicate B, commercially available zeolites A and B (samplesH-2 and H-3) were similarly tested as comparative samples. Obtainedresults are shown in Table 3.

                                      Table 2                                     __________________________________________________________________________    Properties of Synthetic Zeolites                                                                 Sample                                                                             Sample                                                                             Sample                                                                             Sample                                      Item               1-3  H-1  H-2  H-3                                         __________________________________________________________________________    Crystal Form       A    A    A    A                                           Crystallization Degree (C.R)                                                                     72   68.1 79.1 80.5                                        Calcium Ion Binding Property (C.I)                                                               145  140  121  110                                         Initial Buffer Capacity (R)                                                                      39.6 38.2 38.6 26.4                                        Buffer Capacity (S)                                                                              177  125  128  69.1                                        Effective Alkali Quantity (Qc)                                                                   3.96 3.9  3.2  1.9                                         Suspension pH      10.7 10.9 10.6 10.4                                        Oil Absorption (O.A)                                                                             58   44   41   42                                          Bulk Density (B.D) 0.38 0.49 0.57 0.7                                         Primary Particle Size (Dp) (μ)                                                                0.4  1.1  2    3                                           Secondary Particle Size Distribution                                          (Ds) (% by weight)                                                            0 - 3 μ         100  50.1 0.1  1.5                                         3 - 4 μ         --   27.3 0.2  3.0                                         4 μ -           --   22.6 99.7 95.5                                        Sedimentation Speed (Vs) (cm/hr)                                                                 0.6  7.1  9.4  37.4                                        Methylene Blue                                                                Adsorbing Property (A.M)                                                                         5    5    5    5                                           Surface Charge                                                                Controlling Property (ED)                                                                        5    4    4    4                                           __________________________________________________________________________

The chemical composition of the synthetic zeolite prepared in thisExample (sample 1-3) is shown in Table 4.

                  Table 4                                                         ______________________________________                                        Chemical Composition of Synthetic Zeolite (Sample 1-3)                        ______________________________________                                        Ignition Loss    17.34 % by weight                                            SiO.sub.2        35.46 % by weight                                            Al.sub.2 O.sub.3 30.46 % by weight                                            Fe.sub.2 O.sub.3  0.04 % by weight                                            CaO               0.11 % by weight                                            MgO               0.04 % by weight                                            Na.sub.2 O       16.55 % by weight                                            Total            100.00 % by weight                                           ______________________________________                                    

The synthetic zeolite obtained in this Example was incorporated into asynthetic detergent, and an artificially contaminated cloth or the likewas washed and the washing power, the re-contamination preventing effectand the rinsing property were tested according to the methods describedbelow.

An instance of a granular synthetic detergent composition containing thesynthetic zeolite obtained in this Example (sample 1-3) is as follows:

    ______________________________________                                        Linear sodium alkyl benzene-                                                                   18 parts by weight                                           sulfonate                                                                     Synthetic zeolite builder*                                                                     20 parts by weight                                           Carboxymethylcellulose                                                                          1 part by weight                                            Sodium silicate   5 parts by weight                                           Sodium carbonate  3 parts by weight                                           Sodium sulfate   42 parts by weight                                           ______________________________________                                    

Details of chemicals used for the above composition and the testsdescribed below are as follows:

(1) Linear sodium alkyl benzene-sulfonate having a molecular weight of345 ± 5, a purity higher than 50%, an unreacted oil content (startingalkyl benzene content) lower than 1%, a sodium sulfate content lowerthan 2% and a water content lower than 2%.

(2) Sodium tripolyphosphate specified in JIS K-1465.

(3) Sodium silicate used was sodium silicate No. 2 specified in JISK-1408.

(4) Sodium carbonate (anhydride) (reagent grade) specified in JISK-8625.

(5) Carboxymethylcellulose having a substitution degree (etherificationdegree) of 0.5 to 0.6, a purity higher than 95% (as the anhydride), asodium chloride content lower than 5% (as the anhydride) and a watercontent lower than 10%.

(6) Sodium sulfate (anhydride) (reagent grade) specified by JIS K-8987.

(7) Calcium chloride (anhydride) (reagent grade) specified by JISK-8122.

The above components were precisely measured and kneaded sufficiently ina mortar by using a pestle, and the mixture was transferred into aporcelein dish and dried in a drier maintained at 105° ± 2° C. until themixture was substantially powdered. Then, the mixture was treated in amortar by using a pestle and the particle size was reduced so that theresulting powder was completely passed through a 350-μ standard sieve(specified in JIS Z-8801). Then, the resulting powdered product wasstored in a desiccator.

Detergent compositions were similarly prepared by using comparativesamples H-1, H-2 and H-3 instead of the synthetic zeolite asterikedabove.

The water content of the resulting granular detergent was measuredaccording to the method specified in JIS K-3362, 5-17-2, and 1.4 g ascalculated as the anhydrous detergent of the sample was preciselymeasured and dissolved in 1 l of washing water (formed by weighing 135mg of calcium chloride precisely to the unit of mg and dissolving itinto water so that the entire volume was 1 l). The resulting solutionwas used as the detergent solution and subjected to the following teststo determine the washing power, re-contamination preventing effect,rinsing property and suspension stability.

A standard detergent for evaluation of the washing power was prepared inthe following manner:

Components indicated below were precisely weighed and kneadedsufficiently by using a mortar and a pestle, and mixture was transferredinto a porcelein dish and dried in a drier maintained at 105 ± 2° C.until the mixture was substantially powdered. The mixture was treated ina mortar by using a pestle and the particle size was reduced so that theresulting powder was completely passed through a 350-μ standard sieve.The resulting powdered product was stored in a desiccator and used asthe standard detergent for determination of the washing power.

Components of the standard detergent for determination of washing power:

    ______________________________________                                        Linear sodium alkyl benzene-                                                                     30 parts by weight                                         sulfonate                                                                     Sodium tripolyphosphate                                                                          17 parts by weight                                         Sodium silicate    10 parts by weight                                         Sodium carbonate    3 parts by weight                                         Carboxymethylcellulose                                                                            1 part by weight                                          Sodium sulfate     58 parts by weight                                         ______________________________________                                    

1. Measurement of Washing Power

(a) Test Cloth

Cotton cloth (white cloth for the dye color fastness test) specified inJIS L-0803.

(b) Contaminated Cloth

The test cloth was cut into pieces having a size of 11 cm × 13 cm, and 2cloth pieces were joined by stitching short sides of the cloth pieceswith a stitching overlap width of 1 cm in each cloth piece so that theweaving directions of both the cloth pieces were in agreement with eachother. Thus, a neckband (11 cm × 24 cm) was prepared.

The so prepared neckband was fixed to a collar of a shirt or othergarment by buttons or an adhesive tape so that the neckband covered thecollar fold. This shirt or garment was worn for 7 days. The resultingsoiled neckband was used for the washing test as the contaminated cloth.

(c) Washing Test

Among soiled neckbands taken out of the shirts or garments, those soiledequally on both the sides with the seam being as the center were chosen,and they were divided into three groups depending on the degree ofcontamination, namely remarkably contaminated, moderately contaminatedand slightly contaminated groups. Five soiled neckbands were chosen fromeach group, and 15 soiled neckbands were tested as one set of soiledneckbands with respect to each detergent sample. Threads were removedfrom the soiled neckbands. One set of 15 soiled unsewn neckband pieceswere dipped in 1 l of a washing solution of the standard detergentmaintained at 30° C. and another set of 15 soiled unsewn neckband pieceswere dipped in 1 l of a washing solution of the sample detergent.Washing was carried out for 10 minutes by using a agitation type washingpower tester (rotation speed = 120 rpm). The washed cloth pieces werelightly squeezed by hands so that the water content was below 200%.Then, the cloth pieces were rinsed with 1 l of a rinsing liquor of 30°C. which had been prepared in advance by weighing 135 mg of calciumchloride precisely to the unit of mg and dissolving it into water sothat the volume was 1 l) by using the same agitation type washing powertester (rotation speed = 120 rpm). The rinsing was continued for 3minutes. This rinsing operation was conducted two times.

The washed cloth pieces were air-dried and every two corresponding clothpieces were joined by stitching the short sides in the same manner asdescribed above. The resulting washed neckbands were ironed and used asspecimens for evaluation of the washing power.

(d) Evaulation of Washing Power

(1) Evaluation method

On white paper were arranged 15 washed neckbands in the order of signs,and according to the method for comparison of surface colors specifiedin JIS Z-8723 6, every washed neckband was compared with the companionneckband washed by the standard detergent. In this manner, the washingpower of the sample detergent was compared with that of the standarddetergent with respect to each specimen neckband with the naked eye. Theevaluation was performed by 3 experts.

(2) Evaluation standard

The degree of the washing effect by the sample detergent was evaluatedaccording to the following scale based on the degree of the washingeffect by the standard detergent:

- 2: apparently inferior

- 1: slightly inferior

0: no substantial difference

+ 1: slightly superior

+ 2: apparently superior

2. Test of Re-Contamination Preventing Effect at Washing

(1) Washing Method

By using the sample detergents, 10 white cotton cloths mentioned aboveand 10 artificially contaminated cloths were washed in the followingmanner:

A beaker having a capacity of 2000 ml was charged with 1000 ml of awashing liquor formed by dissolving the sample detergent into waterhaving a hardness of 5° DH so that the detergent concentration was0.14%. Then, the above 10 white cloths and 10 contaminated cloths wereimmersed in the washing liquor. Washing was conducted at 30° C. for 10minutes at a rotation number of 120 rpm.

Then, the washed cloths were rinsed with 1000 ml of water having ahardness of 5° DH at 30° C. for 10 minutes at a rotation speed of 120rpm. This rinsing operation was conducted twice. The rinsed cloths wereair-dried and ironed, and they were used as specimens for evaluation ofthe re-contamination preventing effect.

(2) Evaluation Method

White cloths were presented to a panel of 20 mens before and after theabove washing test, and contamination was examined with the naked eyeand evaluated according to a 5-staged scale, in which "5" indicates nocontamination (same as the white cloth before washing) and "1" indicatesthe same contamination degree as that of the artificially contaminatecloth. Accordingly, a value closer to 5 indicates a higherre-contamination preventing effect.

3. Test of Rinsing Property

A glass beaker having a diameter of about 107 mm, a height of 148 mm anda capacity of 1 liter was charged with 1 l of warm water maintained at30° ± 2° C., and 2.5 g of the sample detergent was dispersed. Then, 5black cotton muslin cloths having a size of 10 cm × 10 cm were put intothe dispersion and agitated for 10 minutes at a rotation speed of 200rpm by using a jar tester. Then, the cloths were taken out from thedispersion, immersed in 500 ml of another warm water maintained at 30° ±2° C. and agitated for 3 minutes at a rotation speed of 200 rpm.

Then, the degree of adhesion of the detergent powder to the black cottonmuslin cloths was examined and evaluated with the naked eye by a panelof 20 mens according to a 5-staged scale, in which "1" indicates thelargest adhesion of the detergent powder and "5" indicates no adhesion(same state as in the black cotton cloth before the test). Namely, avalue closer to 5 indicates less adhesion of the detergent powder afterrinsing and a better rinsing property.

4. Measurement of Suspension Stability

A beaker was charged with 1000 ml of deionized water maintained at 20° ±2° C. and 1.5 g of the sample detergent was added thereto. The mixturewas agitated at 120 rpm for 5 minutes by a jar tester to disperse thedetergent in water. Immediately, the suspension was quickly flown into agraduated cylinder having a height of 22.5 cm and a diameter of 2.6 cmso that the suspension reached a scale mark of 100 ml (the height of thescale mark from the bottom being 18.7 cm). The suspension was allowed tostand still for 30 minutes, and the height (cm) of the layer of thesupernatant was measured and multiplied by 2. The suspension stabilitywas expressed in terms of the thus obtained value (cm/hr). Accordingly,a lower value indicates a higher suspension stability.

5. Measurement of Powder Falling Property

Test cloths were washed according to the same washing method asdescribed above with respect to the measurement of the washing power.This washing operation was conducted 5 times. Then, the test cloths wererinsed, air-dried and ironed. For this test, 15 test cloths were usedfor each sample detergent.

The fifteen test cloths were rubbed by hands on black paper so thatwhite fine particles adhering to surfaces, seams and other parts of thetest cloths were caused to fall on the black paper. The degree of powderfalling was examined with the naked eye. The evaluation was performed by3 experts.

The powder falling property was evaluated according to the followingscale based on the powder falling property of the above-mentionedstandard detergent:

- 2: apparently inferior

- 1: slightly inferior

0: no substantial difference

+ 1: slightly superior

+ 2: apparently superior

Results of the foregoing tests made on the detergent containing thesynthetic zeolite of Example 1 and the above-mentioned comparativezeolites are shown in Table 5.

                  Table 5                                                         ______________________________________                                               Detergent                                                                             Detergent Detergent Detergent                                         Sample 1-4                                                                            Sample 1-5                                                                              Sample 1-6                                                                              Sample 1-7                                 ______________________________________                                        Zeolite  1-3       H-1       H-2     H-3                                      builder                                                                       used                                                                          Washing  + 2       - 1       - 2     - 2                                      power                                                                         Re-      5         4         3       2                                        contamination                                                                 preventing                                                                    effect                                                                        Rinsing  4.6       3         1.4     1.2                                      property                                                                      Suspension                                                                             0.3       6         14      18                                       stability                                                                     Powder   + 2       - 1       - 2     - 2                                      falling                                                                       property                                                                      ______________________________________                                    

From the results shown in Table 5, it will readily be understood thatthe synthetic zeolite having a primary particle size of 0.4 μ, asecondary particle size distribution range of 0 to 3 μ, a buffercapacity (S) of 177 ml/100 g, a crystallization degree of 72% and acalcium ion binding property of 145 mg/g, which was prepared in Example1 according to this invention, is very effective as a detergent builder.

EXAMPLE 2

This Example illustrates influences of the amount of the alkali metalhydroxide that is used for the pre-treatment of activated silica.

The activated silica slurry sample 1-2 prepared in Example 1 byacid-treating the clay mineral was treated with sodium hydroxide ofgrade 1 in the following manner.

Each of 10 glass beakers having a capacity of 1 liter was charged with600 g of the activated silica slurry sample 1-2 obtained in Example 1.Sodium hydroxide (NaOH) was added into 9 beakers in amounts of 160 g, 54g, 40 g, 32 g, 23 g, 16 g, 11 g, 8 g and 0.33 g, respectively, while nosodium hydroxide was added to the remaining one beaker. The treatmentwas conducted at 90° C. under agitation to form alkali metalpolysilicate compositions in which the Na₂ O/SiO₂ molar ratios were 1/1,1/3, 1/4, 1/5, 1/7, 1/10, 1/15, 1/20 and 1/500, respectively.

The alkali metal polysilicate composition in which the Na₂ O/SiO₂ molarratio was 1/1 was kept substantially in the solution state.

The activated silica slurry (no sodium hydroxide was added) and the soformed alkali metal polysilicate compositions were mixed with a solutionof sodium aluminate (having an Al₂ O₃ concentration of 19.09% and an Na₂O concentration of 22.49%) and sodium hydroxide to form gelatinousslurries of sodium aluminosilicate. In each run, the composition wasadjusted so that the SiO₂ /Al₂ O₃ molar ratio was 2.0 and the CA valuewas 1.62 mole %. Each slurry was reacted under heating at 90° C. for 6hours to crystallize out a synthetic zeolite.

There were thus obtained the following synthetic zeolites; namely sampleH-4 (no sodium hydroxide was added), sample H-5 (the Na₂ O/SiO₂ molarratio at the pre-treatment was 1/1), sample 2-1 (the Na₂ O/SiO₂ molarratio at the pre-treatment was 1/3) and samples 2-2, 2-3, 2-4, 2-5, 2-6,2-7 and 2-8 (the Na₂ O/SiO₂ molar ratios at the pre-treatment were 1/4,1/5, 1/7, 1/10, 1/15, 1/20 and 1/500, respectively).

Properties of the so obtained synthetic zeolites were determined in thesame manner as described in Example 1 to obtain results shown in Table6.

                                      Table 6                                     __________________________________________________________________________                           Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample             Item                   H-4 H-5 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8                __________________________________________________________________________    Crystal Form           A   A   A   A   A   A   A   A   A   A                  Crystallization Degree (CR)                                                                          68  75  74  73  71  72  72  71  71  68                 Calcium Ion Binding Property (CI)                                                                    120.0                                                                             135.4                                                                             135.4                                                                             135.4                                                                             135.4                                                                             138.2                                                                             140.9                                                                             140.9                                                                             140.9                                                                             138.1              Initial Buffer Capacity (R)                                                                          42.0                                                                              44.9                                                                              42.2                                                                              42.2                                                                              42.2                                                                              42.2                                                                              42.2                                                                              39.6                                                                              42.2                                                                              55.1               Buffer Capacity (S)    120 119 142 139 147 143 153 143 161 136.5              Effective Alkali Quantity (Qc)                                                                       2.60                                                                              2.57                                                                              2.83                                                                              2.85                                                                              3.08                                                                              3.33                                                                              3.50                                                                              3.46                                                                              3.59                                                                              3.02               Suspension pH          10.2                                                                              10.2                                                                              10.3                                                                              10.3                                                                              10.5                                                                              10.6                                                                              10.6                                                                              10.6                                                                              10.6                                                                              10.1               Oil Absorption (OA)    43.0                                                                              42.0                                                                              47.0                                                                              47.0                                                                              48.7                                                                              55.0                                                                              58.8                                                                              59.5                                                                              60.5                                                                              63.5               Bulk Density (BD)      0.54                                                                              0.56                                                                              0.54                                                                              0.51                                                                              0.50                                                                              0.50                                                                              0.42                                                                              0.38                                                                              0.38                                                                              0.40               Primary Particle Size (Dp)(μ)                                                                     1.1 2.3 1   0.9 0.8 0.8 0.5 0.4 0.4 0.6                Secondary Particle Size Distri-                                               bution (Ds) (% by weight)                                                     0-3 μ               24.2                                                                              29.8                                                                              56.8                                                                              84.4                                                                              87.3                                                                              94.2                                                                              95.1                                                                              98.2                                                                              100.0                                                                             56.4               3-4 μ               45.5                                                                              25.1                                                                              20.0                                                                              15.6                                                                              12.7                                                                              5.8 4.9 1.8 --  43.6               4 μ                 30.3                                                                              45.1                                                                              23.2                                                                              --  --  --  --  --  --  --                 Sedimentation Speed (Vs)                                                                             4.3 5.0 3.5 1.8 1.6 0.8 0.4 0.3 0.3 0.9                Methylene Blue Adsorbing                                                                             5   5   5   5   5   5   5   5   5   5                  Property (AM)                                                                 Surface Charge Controlling                                                                           5   5   5   5   5   5   5   5   5   5                  Property (ED)                                                                 __________________________________________________________________________

Detergents were prepared by using the above synthetic zeolites in thesame manner as described in Example 1, and the washing power,re-contamination preventing effect, rinsing property, suspensionstability and powder falling property were tested in the same manner asdescribed in Example 1 to obtain results shown in Table 7.

                                      Table 7                                     __________________________________________________________________________                    Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                    2-9 2-10                                                                              2-11                                                                              2-12                                                                              2-13                                                                              2-14                                                                              2-15                                                                              2-16                                                                              2-17                                                                              2-18                      __________________________________________________________________________    Sample Number of Zeolite                                                                      H-4 H-5 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8                       Builder Used                                                                  Washing Power   - 1 - 2 + 0 + 1 + 2 + 2 + 2 + 2 + 1 + 0                       Re-Contamination Preventing                                                   Effect          3   3   3.5 4   4.9 5   5   5   5   5                         Rinsing Property                                                                              2   1.2 3   3.5 4.5 4.5 4.6 4.6 4.6 4.5                       Suspension Stability                                                                          0.4 0.8 0.6 0.4 0.4 0.3 0.2 0.2 0.2 0.3                       Powder Falling Property                                                                       - 1 - 2 + 0 + 1 + 2 + 2 + 2 + 2 + 1 + 0                       __________________________________________________________________________

EXAMPLE 3

This Example illustrates influences of conditions of the pre-treatmentof activated silica.

(A) To 600 g of the activated silica slurry sample 1-2 prepared inExample 1 was added 7.6 g of sodium hydroxide so that the Na₂ O/SiO₂molar ratio was 1/21. The mixture was aged under agitation for 15 hoursat 20° ± 2° C. to form an alkali metal polysilicate slurry. Then, sodiumaluminate was added to the slurry so that the Na₂ O/SiO₂ molar ratio was1.0, the SiO₂ /Al₂ O₃ molar ratio was 2.0 and the H₂ O/Na₂ O molar ratiowas 60. Then, the resulting gelatinous slurry of sodium aluminosilicatewas heated at 90° C. to effect crystallization and obtain a syntheticzeolite (sample 3-1).

(B) To 100 g of the activated silica sample 1-1 (having a water contentof 50%) described in Example 1 was added 3.2 g of sodiium hydroxide sothat the Na₂ O/SiO₂ molar ratio was 1/21. The mixture was sufficientlykneaded in a mortar and dried in a drier maintained at 110° C. Then,water was added to the resulting alkali metal polysilicate so that theSiO₂ concentration was 10% by weight, and the mixture was pulverized ina ball mill. Then, sodium aluminate was added to the resulting alkalimetal polysilicate slurry so that the Na₂ O/SiO₂ molar ratio was 1.0,the SiO₂ /Al₂ O₃ molar ratio was 2.0 and the H₂ O/Na₂ O molar ratio was60. The resulting gelatinous slurry of sodium aluminosilicate was heatedat 90° C. to effect crystallization and obtain a synthetic zeolite(sample 3-2).

Physical properties of these zeolite samples 3-1 and 3-2 were determinedin the same manner as described in Example 1 to obtain results shown inTable 8.

                  Table 8                                                         ______________________________________                                                                 Sample  Sample                                       Item                     3-1     3-2                                          ______________________________________                                        Crystal Form             A       A                                            Crystallization Degree (CR)                                                                            69.9    70                                           Calcium Ion Binding Property (CI)                                                                      143     135                                          Initial Buffer Capacity (R)                                                                            41.8    40.1                                         Buffer Capacity (S)      176.8   158                                          Effective Alkali Quantity (Qc)                                                                         3.97    3.77                                         Suspension pH            10.6    10.6                                         Oil Absorption (OA)      59.0    50                                           Bulk Density (BD)        0.395   0.42                                         Primary Particle Size (Dp) (μ)                                                                      0.4     0.7                                          Secondary Particle Size Distri-                                               bution (Ds) (% by weight)                                                     0 - 3 μ               100     88                                           3 - 4 μ               --      12                                           4 μ -                 --      --                                           Sedimentation Speed (Vs) 0.6     0.7                                          Methylene Blue Adsorbing 5       5                                            Property (AM)                                                                 Surface Charge Controlling                                                                             5       5                                            Property (ED)                                                                 ______________________________________                                    

Detergents were prepared by using the above synthetic zeolite samples3-1 and 3-2 in the same manner as described in Example 1, and thewashing power, re-contamination preventing effect, rinsing property,suspension stability and powder falling property were determined in thesame manner as described in Example 1 to obtain results shown in Table9.

                  Table 9                                                         ______________________________________                                                           Sample  Sample                                                                3-3     3-4                                                ______________________________________                                        Sample Number of Zeolite Used                                                                      3-1       3-2                                            Washing Power        + 2       + 2                                            Re-Contamination Preventing Effect                                                                 5         5                                              Rinsing Property     4.6       4.6                                            Suspension Stability 0.3       0.4                                            Powder Falling Property                                                                            + 2       + 2                                            ______________________________________                                    

EXAMPLE 4

This Example illustrates an embodiment comprising drying and pulverizingactivated silica obtained by acid-treatment of the clay, adding water tothe resulting powder of activated silica to form a slurry, adding acommercially available sodium silicate solution No. 3 to the slurry toeffect the pre-treatment, adding a solution of sodium aluminate to theresulting sodium polysilicate and crystallizing out a zeolite.

The sodium silicate solution No. 3 was mixed with the activated silicaslurry sample 1-2 prepared in Example 1 so that the Na₂ O/SiO₂ molarratio in the resulting composition was 1/4, 1/6, 1/8, 1/10, 1/15, 1/20or 1/500.

Then, a sodium aluminate solution having an Al₂ O₃ concentration of19.09% and an Na₂ O concentration of 22.49% was added together withwater and sodium hydroxide to the above alkali polysilicate compositionso that the Na₂ O/SiO₂ molar ratio was 1.32, the SiO₂ /Al₂ O₃ molarratio was 1.94 and the H₂ O/Na₂ O molar ratio was 61.8. The resultinggelatinous slurry of sodium aluminosilicate was heated and reacted at90° C. for 6 hours to crystallize out a synthetic zeolite.

There were thus obtained synthetic zeolites; namely, sample 4-1 (the Na₂O/SiO₂ molar ratio was 1/4 in the alkali polysilicate composition) andsamples 4-2, 4-3, 4-4, 4-5, 4-6 and 4-7 (the Na₂ O/SiO₂ molar ratios inthe alkali polysilicate compositions were 1/6, 1/8, 1/10, 1/15, 1/20 and1/500, respectively).

For comparison, in the same manner as described above, the above sodiumaluminate solution was added to the sodium silicate solution No. 3 and asynthetic zeolite (sample H-6 ) was prepared from the resulting sodiumaluminosilicate gelatinuous slurry.

Another comparative zeolite builder (sample H-7) was prepared accordingto the teaching of Japanese Patent Application Laid-Open SpecificationNo. 12381/75 in the following manner:

Powder of activated silica was added to the sodium silicate solution No.3 to form sodium silicate having a composition coresponding to Na₂O.6SiO₂, and the sodium silicate was added together with water andsodium hydroxide to sodium aluminate so that the Na₂ O/SiO₂ mole ratiowas 1.32, the SiO₂ /Al₂ O₃ molar ratio was 1.94 and the H₂ O/Na₂ O molarratio was 61.8 in the resulting sodium aluminosilicate gel. Then, themixture was agitated and blended at a rotation speed of 10000 to 12000rpm by using an agitating mixer (Model VA-853 manufactured by HitachiSeisakusho K. K.) The resulting sodium aluminosilicate gel slurry washeated and reacted at 80° C. for 24 hours under agitation to form asynthetic zeolite (sample H-7).

Properties of these zeolites were determined in the same manner asdescribed in Example 1 to obtain results shown in Table 10.

                                      Table 10                                    __________________________________________________________________________                        Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                    Item                H-6 H-7 4-1 4-2 4-3 4-4 4-5 4-6 4-7                       __________________________________________________________________________    Crystal Form        A   A   A   A   A   A   A   A   A                         Crystallization Degree (CR)                                                                       78  80  74  71  70  68  65  65  62                        Calcium Ion Binding Property (CI)                                                                 133 110 136 140 142 143 136 135 128                       Initial Buffer Capacity (R)                                                                       34.0                                                                              23.6                                                                              39.6                                                                              37  38  38.1                                                                              38  37  37                        Buffer Capacity (S) 116.1                                                                             68.3                                                                              154.1                                                                             150.4                                                                             150.0                                                                             148.1                                                                             150.1                                                                             148 146                       Effective Alkali Quantity (Qc)                                                                    2.5 1.3 3.8 3.8 3.78                                                                              3.78                                                                              3.8 3.8 3.71                      Suspension pH       10.3                                                                              9.5 10.5                                                                              10.4                                                                              10.4                                                                              10.4                                                                              10.4                                                                              10.5                                                                              10.4                      Oil Absorption (OA) 43.1                                                                              35.5                                                                              50.5                                                                              50.1                                                                              50.1                                                                              55.1                                                                              55.0                                                                              56.0                                                                              54.5                      Bulk Density (BD)   0.51                                                                              0.62                                                                              0.479                                                                             0.48                                                                              0.39                                                                              0.38                                                                              0.38                                                                              0.39                                                                              0.4                       Primary Particle Size (Dp) (μ)                                                                 2.1 5.4 1.0 1.0 0.8 0.6 0.6 0.7 1.0                       Secondary Particle Size Distri-                                               bution (Ds) (% by weight)                                                     0 - 3 μ          12.3                                                                              0.5 48  63  100 100 100 100 84                        3 - 4 μ          26.6                                                                              6.3 52  37  --  --  --  --  16                        4 μ -            61.1                                                                              93.2                                                                              --  --  --  --  --  --  --                        Sedimentation Speed (Vs)                                                                          15  37.4                                                                              9   9   1.8 0.8 0.8 0.8 8                         Methylene Blue Adsorbing                                                      Property (AM)       5   5   5   5   5   5   5   5   5                         Surface Charge Controlling Pro-                                               perty (ED)          4   3   5   5   5   5   5   5   5                         __________________________________________________________________________

Detergents were prepared by using the above synthetic zeolites in thesame manner as described in Example 1, and the washing power,re-contamination preventing effect, rinsing property, suspensionstability and powder falling property of these detergents weredetermined in the same manner as described in Example 1 to obtainresults shown in Table 11.

                                      Table 11                                    __________________________________________________________________________                        Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                        4-8 4-9 4-10                                                                              4-11                                                                              4-12                                                                              4-13                                                                              4-14                                                                              4-15                                                                              4-16                      __________________________________________________________________________    Sample Number of Zeolite Used                                                                     H-6 H-7 4-1 4-2 4-3 4-4 4-5 4-6 4-7                       Washing Power       - 2 - 2 + 0 + 0 + 1 + 1 + 2 + 2 + 1                       Re-Contamination Preventing                                                   Effect              3   1   4   4   5   5   5   5   5                         Rinsing Property    1.2 1   3.5 4.0 4.6 4.6 4.6 4.6 4.0                       Suspension Stability                                                                              15  37.4                                                                              5   0.5 0.2 0.2 0.2 0.3 0.4                       Powder Falling Property                                                                           - 2 - 2 + 0 + 0 + 1 + 1 + 2 + 2 + 1                       __________________________________________________________________________

EXAMPLE 5

In this Example, the same acid clay as used in Example 1, that wasproduced in Nakajo, Niigata Prefecture, Japan, was treated with sulfuricacid under various conditions.

The starting acid clay was molded in columns having a diameter of 5 mmand a length of 5 to 20 mm, and 76.5 g each of the molded clay ascalculated as the dried product was charged into four conical beakershaving a capacity of 500 ml. Then, 200 ml of sulfuric acid having aconcentration of 50% by weight was added to each beaker. Then, thegranular clay was acid-treated at 90° C. for 2, 8, 20 or 30 hours.Sulfates of basic components that had reacted with sulfuric acid werewashed away and removed by decantation using dilute sulfuric acid andwater. The recovered acid-treated clay was washed with water untilsulfate ion was not detected at all. Thus, there were obtained4acid-treated clays. The starting acid clay was designated as sample5-1, and products acid-treated for 2, 8, 20 and 30 hours were designatesas samples 5-2, 5-3, 5-4 and 5-5, respectively.

These samples 5-1 to 5-5 were subjected to the X-ray diffractionanalysis and the degrees of destruction of crystal structures (DC, %)were determined from the diffraction peaks. Further, each sample wassubjected to the chemical analysis. Obtained results are shown in Table12.

                                      Table 12                                    __________________________________________________________________________                     Sample Sample                                                                            Sample Sample Sample                                               5-1    5-2 5-3    5-4    5-5                                 __________________________________________________________________________    Acid Treatment Time (hours)                                                                    0(untreated)                                                                         2   8      20     30                                  X-Ray Diffraction Pattern                                                                      FIG. 8 FIG. 9                                                                            FIG. 10                                                                              FIG. 11                                                                              --                                  Composition (% by weight)                                                     ignition loss    5.27   5.5 5.6    3.11   3.60                                SiO.sub.2        72.1   76.22                                                                             84.2   94.10  94.21                               Al.sub.2 O.sub.3 14.23  11.3                                                                              7.1    1.67   1.30                                Fe.sub.2 O.sub.3 3.87   3.18                                                                              1.4    0.46   0.43                                MgO              3.47   2.8 1.2    0.31   0.31                                CaO              1.06   1.0 0.5    0.07   0.15                                SiO.sub.2 /Al.sub.2 O.sub.3 Molar Ratio                                                        8.6    11.47                                                                             20.2   95.8   123.2                               AAI              8      16  39     37     37                                  [001] DC (%)     100    18  undetectable                                                                         undetectable                                                                         undetectable                        [020] DC (%)     100    80  15     5      3                                   __________________________________________________________________________

The above granular acid-treated products were treated in order to attaina particle size distribution suitable for the production of an alkalipolysilicate for the synthesis of a zeolite builder. More specifically,the untreated starting clay or acid-treated product was put into ahousehold mixer (Mode VA-853 manufactured by Hitachi Seisakusho K. K.)and water was added thereto so that the solid concentration was 20% byweight, and the mixture was agitated and pulverized for 40 minutes andsieved by using a 270-Typer mesh sieve. Thus, a slurry of the untreatedstarting clay or acid-treated product having the particle size thusadjusted was obtained. The particle size distribution (% by weight) wasdetermined to obtain results shown in Table 13. With respect to sample5-4 as a typical instance, the secondary particle size distribution (Ds)was examined more detailedly to obtain results shown in Table 14.

                  Table 13                                                        ______________________________________                                        Particle Size                                                                 Distribution                                                                            Sample   Sample  Sample Sample                                                                              Sample                                (% by weight)                                                                           5-1      5-2     5-3    5-4   5-5                                   ______________________________________                                        0 - 5  μ                                                                             65.4     65.1    64.8   65.0  64.9                                  5 - 20 μ                                                                             34.6     34.9    35.2   35.0  35.1                                  above 20 μ                                                                           0        0       0      0     0                                     ______________________________________                                    

                                      Table 14                                    __________________________________________________________________________    Secondary Particle Size                                                       Distribution (Ds) (% by                                                                   0-1 μ                                                                          1-2 μ                                                                          2-3 μ                                                                          3-4 μ                                                                          4-5 μ                                                                          5-6 μ                                                                          6-7 μ                                                                          7-8 μ                                                                          8-9 μ                                                                          9-10 μ                     weight)                                                                       Sample 5-4  4.6 10.3                                                                              19.2                                                                              20.1                                                                              10.8                                                                              10.5                                                                              9.8 7.5 7.2 0                             __________________________________________________________________________

Then, 200 g each of samples 5-1 to 5-5 were charged into 1-litercapacity beakers, respectively, and 3 g, 3.2 g, 3.6 g, 4 g and 4 g ofsodium hydroxide were added to samples 5-1 to 5-5, respectively. Eachmixture was aged at 60° C. under agitation for 2 hours to obtain analkali metal polysilicate slurry.

As one of conditions for the synthesis of a synthetic zeolite, thefollowing composition expressed in terms of oxide molar ratios waschosen:

Na₂ SiO₂ = 1.0

SiO₂ /Al₂ O₃ = 2.0

H₂ /Na₂ O = 60

In order to attain the above molar ratios, necessary amounts of analumina component and alkali metal and water components for the reactionwere added to the above slurries of the acid-treated clays (the contentsof SiO₂ and Al₂ O₃ differed depending on the acid treatment conditions).More specifically, a commercially available sodium aluminate solution(having an Na₂ O content of 21.0% and an Al₂ O₃ content of 18.8%) wasmixed with commercially available caustic soda (NaOH) and water so thatthe above composition was attained, and the mixture was filtered toobtain a purified liquid mixture. The acid-treated clay slurry and theresulting liquid mixture were charged in a beaker having a capacity of 2liters so that the amount of the reaction mixture was about 1.5 liters.The mixture was agitated at 20° C., whereby the mixture once passedthrough a gelled state and was then converted to a homogeneous slurry.The temperature was elevated to 95° C. and the mixture was agitated for3 hours to effect reaction and form crystalline particles of a zeolite.The reaction mixture was filtered by a suction filter and washed withdeionized water. The filter cake recovered was dried in a driermaintained at 110° C. Thus, there were obtained 5 synthetic zeolites,samples H-8, H-9, 5-6, 5-7 and 5-8, from the above samples 5-1 to 5-5,respectively.

Properties of the so obtained zeolites were determined in the samemanner as described in Example 1 to obtain results shown in Table 15.

                                      Table 15                                    __________________________________________________________________________                         Sample                                                                            Sample                                                                             Sample                                                                            Sample                                                                            Sample                                  Item                 H-8 H-9  5-6 5-7 5-8                                     __________________________________________________________________________    Crystal Form         A   A + Na                                                                             A   A   A                                       Crystallization Degree (CR)   67  72  73                                      Calcium Ion Binding Property (CI)                                                                  62  81   116 142 142                                     Initial Buffer Capacity (R)                                                                        34  42   55  39  42                                      Buffer (S)           109 115  180 178 179                                     Effective Alkali Quantity (Qc)                                                                     4.1 4.0  3.8 3.6 3.6                                     Suspension pH        11.0                                                                              10.8 10.6                                                                              10.7                                                                              10.7                                    Oil Absorption (OA)  38  40   49  58  58                                      Bulk Density (BD)    0.53                                                                              0.51 0.42                                                                              0.38                                                                              0.39                                    Primary Particle Size (Dp)(μ)                                                                   2.0 1.5  0.6 0.4 0.3                                     Secondary Particle Size Distribut-                                            tion (Ds) (% by weight)                                                       0 - 3 μ           75  87   96  98  100                                     3 - 4 μ           12  9    4   2   --                                      4 μ -             13  4    --  --  --                                      Sedimentation Speed (Vs)                                                                           30.1                                                                              25.0 1.0 0.6 0.5                                     Methylene Blue Adsorbing Property (AM)                                                             4   5    5   5   5                                       Surface Charge Controlling Property (ED)                                                           4   4    5   5   5                                       __________________________________________________________________________

Detergents were prepared by using the above zeolites in the same manneras described in Example 1, and properties of the resulting detergentswere tested in the same manner as described in Example 1 to obtainresults shown in Table 16.

                  Table 16                                                        ______________________________________                                                  Sample                                                                              Sample  Sample  Sample                                                                              Sample                                            5-9   5-10    5-11    5-12  5-13                                    ______________________________________                                        Sample Number of                                                                          H-8     H-9     5-6   5-7   5-8                                   Zeolite Used                                                                  Washing Power                                                                             -2      -2      +2    +2    +2                                    Re-Contamination                                                                          3       3       5     5     5                                     Preventing Effect                                                             Rinsing Property                                                                          2       3.5     4.5   4.5   4.5                                   Suspension Stab-                                                                          15      13      0.3   0.3   0.3                                   lity                                                                          Powder Falling                                                                            -2      -2      +2    +2    +2                                    Property                                                                      ______________________________________                                    

EXAMPLE 6

In this Example, as the starting smectite clay there were chosen (1)sub-bentonite produced in Tsugawa, Niigata Prefecture, Japan, (2) whiteclay produced in Sanko, Niigata Prefecture, Japan and (3) sub-bentoniteproduced in chito, USA, they were acid-treated and synthetic zeoliteswere prepared from slurries of fine particles of the acid-treated clays.

To 500 g of the starting clay was added 9500 g of water, and the mixturewas pulverized in a ball mill. The resulting slurry was subjected toclassification and hydraulic elutriation by using a liquid cyclone toremove impurities and subjected to evaporation to adjust the watercontent to 50%. In a ball mill having a capacity of 7.5 liters, 325 g ofconcentrated sulfuric acid was added to the clay slurry to form a creamymixture. The mixture was heated at 180° C. in a steam atmosphere for 3hours to effect the acid treatment. Sulfates formed by the reaction werewashed away and removed, and the residue was washed with water until nosulfate ion was detected, to obtain an acid-treated clay.

Results of the chemical analysis and X-ray diffractions analysis of thestarting clay and acid-treated clay are shown in Table 17.

                                      Table 17                                    __________________________________________________________________________                  Sample 6-1   Sample 6-2                                                       Sub-bentonite produced in                                                                  White clay produced in                                                                     Sample 6-3                                          Tsugawa, Niigata Prefec-                                                                   Sanko, Niigata Perfec-                                                                     Sub-bentonite produced in                           ture,Japan   ture, Japan  Chito, USA                            Clay          Untreated                                                                           Acid-Treated                                                                         Untreated                                                                           Acid-Treated                                                                         Untreated                                                                           Acid-Treated                    __________________________________________________________________________    Composition (% by weight)                                                     ignition loss 3.65  4.3    11.85 8.5    7.14  6.91                            Sio.sub.2     73.96 88.31  53.11 83.49  60.37 86.01                           Al.sub.2 O.sub.3                                                                            15.22 4.31   30.17 6.21   24.83 4.10                            Fe.sub.2 O.sub.3                                                                            2.72  1.30   3.95  1.10   2.74  1.08                            CaO           1.12  0.68   0.52  0.22   1.66  0.80                            MgO           2.42  1.1    1.31  0.48   3.22  1.10                            SiO.sub.2 / Al.sub.2 O.sub.3 Molar Ratio                                                    8.26  34.9   3.0   22.9   4.13  35.7                            AAI           2     24     7     33     1.5   40                              [001] DC (%)  100   undetectable                                                                         100   undetectable                                                                         100   undetectable -[020] DC                                                        (%) 100 15 100 7 100 15         __________________________________________________________________________

Water was added to each acid-treated product so that the solidconcentration was 20% by weight, and the mixture was wet-pulverized in aball mill to obtain a fine slurry. Each slurry was charged in a glassbeaker having a capacity of 1 liter. Then, 9.7 g, 9.2 g and 9.5 g ofsodium hydroxide were added to slurries of acid-treated products ofsamples 6-1, 6-2 and 6-3, respectively, under agitation, and eachmixture was aged at 60° C. for 2 hours to obtain an alkali metalpolysilicate slurry.

Then, alkali metal aluminosilicate slurries were prepared from the aboveslurries in the same manner as described in Example 1 while adjustingamounts added of sodium aluminate and NaOH based on the analysis valuesof the acid-treated products so as to attain the following composition:

Na₂ O/SiO₂ molar ratio = 1.26

SiO₂ /Al₂ O₃ molar ratio = 2.0

H₂ O/Na₂ O molar ratio = 50

Then, in the same manner as described in Example 1, the crystallizationreaction was carried out, and the reaction product was recovered throughwashing and drying. Properties of the so obtained zeolites weredetermined in the same manner as described in Example 1 to obtainresults shown in Table 18. Samples 6-4, 6-5 and 6-6 in Table 18 arethose obtained from acid-treated clay samples 6-1, 6-2 and 6-3,respectively.

                  Table 18                                                        ______________________________________                                                          Sample   Sample   Sample                                    Item              6-4      6-5      6-6                                       ______________________________________                                        Crystal Form      A        A        A                                         Crystallization Degree (CR)                                                                     70       71       69                                        Calcium Ion Binding Pro-                                                                        135      138      132                                       perty (CI)                                                                    Initial Buffer Capacity (R)                                                                     38       36       39                                        Buffer Capacity (S)                                                                             165      156      168                                       Effective Alkali Quantity (Qc)                                                                  3.5      3.8      3.9                                       Suspension pH     10.7     10.6     10.8                                      Oil Absorption (OA)                                                                             54       52       56                                        Bulk Density (BD) 0.42     0.45     0.41                                      Primary Particle size (Dp)(μ)                                                                0.8      0.7      0.8                                       Secondary Particle Size                                                       Distribution(Ds)(% by weight)                                                 0 - 3 μ        91       93       90                                        3 - 4 μ        9        7        10                                        4 μ -          --       --       --                                        Sedimentation Speed (Vs)                                                                        0.7      0.8      0.6                                       Methtlene Blue Adsorbing                                                                        5        5        5                                         Property (AM)                                                                 Surface Charge Controlling                                                                      5        5        5                                         Property (ED)                                                                 ______________________________________                                    

Detergents were prepared by using the above zeolites in the same manneras described in Example 1, and properties of the resulting detergentswere determined in the same manner as in Example 1 to obtain resultsshown in Table 19.

                  Table 19                                                        ______________________________________                                                        Sample Sample   Sample                                                        6-7    6-8      6-9                                           ______________________________________                                        Sample Number of Zeolite Used                                                                   6-4      6-5      6-6                                       Washing Power     +1       +1       +1                                        Re-Contamination Preventing                                                   Effect            5        5        5                                         Rinsing Property  4.5      4.5      4.5                                       Suspension Stability                                                                            0.4      0.4      0.4                                       Powder Falling Property                                                                         +1       +1       +1                                        ______________________________________                                    

As will be apparent from the results shown in Table 19, according tothis invention, synthetic zeolites excellent as builders for detergentscan be obtained even if the kind of the starting smectite clay or theacid treatment condition is changed.

EXAMPLE 7

Water was added to 500 g of the same acid clay as used in Example 1,that was produced in Nakajo, Niigata Prefecture, Japan, to form 5 Kg ofa mixture, and the mixture was sufficiently pulverized in a ball milland subjected to classification and hydraulic elutriation by using aliquid cyclone. Water was removed from the resulting clay slurry (sample7-1) by filtration and drying so that the water content was reduced toabout 60 %. The slurry was charged in a lead-lined vessel together withsulfuric acid having a concentration of about 40 %, and the mixture washeated at 90° C. under agitation for 20 hours to effect acid treatment,followed by filtration and water washing. Then, 13.4 g of sodiumhydroxide was added to 100 g (as the dry product) of the so obtainedactivated silica (sample 7-2) at 60° C. under agitation and thetreatment was conducted for 2 hours to obtain an alkali metalpolysilicate slurry (sample 7-3).

Particle size distributions (Ds ) of the clay slurry (sample 7-1 ), theactivated silica slurry (sample 7-2 ) and the alkali metal polysilicateslurry (sample 7-3 ) are shown in Table 20.

                  Table 20                                                        ______________________________________                                        Particle Size Distri-                                                                        Sample    Sample    Sample                                     bution (%)     7-1       7-2       7-3                                        ______________________________________                                        0 - 5  μ    70        78        84                                         5 - 20 μ    30        22        16                                         above 20 μ  0         0         0                                          ______________________________________                                    

A sodium aluminate solution and commercially available sodium hydroxidewere added to the alkali metal polysilicate slurry so that the followingcomposition (molar ratios ) was attained:

Na₂ O/SiO₂ = 1.2

SiO₂ /Al₂ O₃ = 2.0

H₂ O/Na₂ O = 50.0

CA value ≈ 1.95 %

The so obtained alkali metal aluminosilicate gelatinous slurry washeated at 90° C. to effect crystallization reaction, and the reactionproduct (sample 7-4 ) was recovered through washing and drying.Properties of the reaction product were determined in the same manner asdescribed in Example 1 to obtain results shown in Table 21.

                  Table 21                                                        ______________________________________                                                                Sample                                                Item                    7-4                                                   ______________________________________                                        Crystal Form            A                                                     Crystallization Degree (CR)                                                                           72                                                    Calcium Ion Binding Property (CI)                                                                     141                                                   Initial Buffer Capacity (R)                                                                           38                                                    Buffer Capacity (S)     170                                                   Effective Alkali Quanty (Qc)                                                                          3.6                                                   Suspension pH           10.8                                                  Oil Absorption (OA)     59                                                    Bulk Density (BD)       0.38                                                  Primary Particle Size (Dp)(μ)                                                                      0.3                                                   Secondary Particle Size Distribu-                                             tion (Ds) (% by weight)                                                       0 - 3 μ              100                                                   3 - 4 μ              --                                                    4 μ -                --                                                    Sedimentation Speed (Vs)                                                                              0.5                                                   Methylene Blue Adsorbing                                                      Property (AM)           5                                                     Surface Charge Controlling                                                    Property (ED)           5                                                     ______________________________________                                    

A detergent was prepared by using the above zeolite as the builder inthe same manner as described in Example 1, and properties of theresulting detergent (sample 7-5 ) were determined in the same manner asdescribed in Example 1 to obtain results shown in Table 22.

                  Table 22                                                        ______________________________________                                                            Sample 7-5                                                ______________________________________                                        Sample Number of Zeolite Used                                                                       7-4                                                     Washing Power         +2                                                      Re-Contamination Preventing                                                                         5                                                       Effect                                                                        Rinsing Property      4.7                                                     Suspension Stability  0.3                                                     Power Falling Proerty +2                                                      ______________________________________                                    

As is seen from the results shown above, according to this invention,even when an alkali metal polysilicate obtained by acid-treating a clayafter refining and pulverization and opre-treating the acid-treated claywith the alkali component is used as the starting material, a syntheticzeolite excellent in washing effects as well as synthetic zeolitesobtained in the preceding Examples can be prepared.

EXAMPLE 8

This Example illustrates another methods for preparing alkali metalaluminosilicate gels. Run (A) (method comprising adding a slurry of analkali metal polysilicate corresponding to Na₂ O.10SiO₂ to an alkalimetal aluminate solution ):

A beaker having a capacity of 2 liters was charged with 1118 g of analkali metal aluminate solution containing 7.4 % of Al₂ O₃ and 7.27 % ofNa₂ O. Water was added to the same alkali metal polysilicate slurry asprepared in Example 1 so that the SiO₂ concentration was 10 %, and 952 gof the resulting slurry was added to the above alkali metal aluminatesolution over a period of about 30 minutes. The mixture was treated inthe same manner as in Example 1 to obtain a homogeneous gelatinousslurry of an alkali metal aluminosilicate.

This alkali metal aluminosilicate slurry was reacted at 85° C. for 4hours to crystallize out a synthetic zeolite. The resulting crystal wasrecovered by filtration, washed with water and dried to obtain asynthetic zeolite (sample 8-1 ). Run (B) (method comprisingsimultaneously adding an alkali metal aluminate solution and an alkalimetal polysilicate to water ):

A beaker having a capacity of 2 liters was charged with 265 g of water,and 892 g of a slurry of an alkali metal polysilicate (corresponding toNa₂ O.10SiO₂ ) having an SiO₂ concentration of 11.2 % by weight and 913g of an alkali metal aluminate solution having an Al₂ O₃ concentrationof 9.1 % by weight were simultaneously added to the content of thebeaker under agitation over a period of about 30 minutes. At the initialstage of the mixing operation, slight increase of the viscosity wasobserved, but both the components were well dispersed in the latterstage and a homogeneous gelatinous slurry was obtained.

In the same manner as in Run (A), the slurry was reacted at 85° C. for 4hours to effect crystallization. The resulting crystal was recovered byfiltration, washed with water and dried to obtain a synthetic zeolite (sample 8-2 ).

Properties of these synthetic zeolites were determined in the samemanner as described in Example 1 to obtain results shown in Table 23.

                  Table 23                                                        ______________________________________                                                               Sample   Sample                                        Item                   8-1      8-2                                           ______________________________________                                        Crystal Form           A        A                                             Crystallization Degree (CR)                                                                          70       70                                            Calcium Ion Bonding Property (CI)                                                                    38       139                                           Initial Buffer Capacity (R)                                                                          36       36                                            Buffer Capacity (S)    168      168                                           Effective Alkali Quanity (Qc)                                                                        3.5      3.5                                           Suspension pH          10.6     10.5                                          Oil Absorption (OA)    52       51                                            Bulk Density (BD)      0.42     0.42                                          Primary Particle Size (Dp)(μ)                                                                     0.4      0.4                                           Secondary Particle Size Distribu-                                             tion (Ds) (% by weight)                                                       0 - 3 μ             98.2     99                                            3 - 4 μ             1.8      1                                             4 μ -               --       --                                            Sedimentation Speed (Vs)                                                                             0.7      0.7                                           Methylene Blue Adsorbing Property (AM)                                                               5        5                                             Surface Charge Controlling                                                    Property (ED)          5        5                                             ______________________________________                                    

Detergents were prepared by using the above synthetic zeolites in thesame manner as described in Example 1, and properties of the resultingdetergents (samples 8-3 and 8-4 ) were determined in the same manner asdescribed in Example 1 to obtain results shown in Table 24.

                  Table 24                                                        ______________________________________                                                           Sample  Sample                                                                8-3     8-4                                                ______________________________________                                        Sample Number of Zeolite Used                                                                      8-1       8-2                                            Washing Power        +2        +2                                             Re-contamination Preventing                                                                        5         5                                              Effect                                                                        Rinsing Property     4.5       4.5                                            Suspension Stability 0.3       0.3                                            Powder Falling Property                                                                            +2        +2                                             ______________________________________                                    

As is apparent from the above results, according to this invention, evenwhen an alkali metal polysilicate is added to an alkali metal aluminateor both the alkali metal salts are simultaneously added to water,synthetic zeolites excellent in washing effects as well as syntheticzeolites obtained in the preceding Examples can be prepared.

EXAMPLE 9

This Example illustrates influences of the alkali concentration of thezeolite-crystallizing-out reaction between sodium aluminate and analkali metal polysilicate formed by subjecting an acid-treated acid clayto the pre-treatment with an alkali metal component.

Each of 3 beakers having a capacity of 1 liter was charged with 300 g ofan alkali metal polysilicate slurry prepared in the same manner as inExample 1, and sodium aluminate comprising 18.54 % of Na₂ O, 19.1 % ofAl₂ O₃ and 62.36 % of H₂ O and commercially available sodium hydroxidewere added to the slurry together with water if necessary, so that thealkali concentration, CA value, was 4, 2.5 and 1.2 mole %. Thecomposition was adjusted so that the Na₂ O/SiO₂ molar ratio was 1.0 andthe SiO₂ /Al₂ O₃ molar ratio was 2.0. The resulting alkali metalaluminosilicate gel was reacted at 95° C. for 3 hours under agitation toform crystalline particles of a synthetic zeolite. The mother liquor wasremoved, and the residue was washed with water and filtered and thefilter cake was recovered. Thus, there were obtained 3 syntheticzeolites, namely sample 9- 1 (prepared from the raw material having a CAvalue of 4 mole %), sample 9-2 (prepared from the raw material having aCA value of 2.5 mole % ) and sample 9-3 (prepared from the raw materialhaving a CA value of 1.2 mole % ). Properties of these zeolites weredetermined in the same manner as described in Example 1 to obtainresults shown in Table 25.

                  Table 25                                                        ______________________________________                                                          Sample   Sample   Sample                                    Item              9-1      9-2      9-3                                       ______________________________________                                        Crystal Form      A        A        A                                         Crystallization Degree (CR)                                                                     64.2     63.5     64.1                                      Calcium Ion Binding Property                                                                    132      135      133                                       (CI)                                                                          Initial Buffer Capacity (R)                                                                     58.1     52.8     42.2                                      Buffer Capcity (S)                                                                              185      172      148                                       Effective Alkali Quantity (Qc)                                                                  4.6      4.68     3.12                                      Suspension pH     10.8     10.9     10.3                                      Oil Absorption (OA)                                                                             68       68.5     75.5                                      Bulk Density (BD) 0.432    0.376    0.283                                     Primary Particle Size (Dp)(μ)                                                                0.2      0.4      1                                         Secondary Particle Size                                                       Distribution (Ds) (% by weight)                                               0 - 3 μ        100      94       82                                        3 - 4 μ        --       6        18                                        4 μ -          --       --       --                                        Sedimentation Speed (Vs)                                                                        0.5      0.6      0.8                                       Methylene Blue Adsorbing                                                                        5        5        5                                         Property (AM)                                                                 Surface Charge Controlling                                                                      5        5        5                                         Property (ED)                                                                 ______________________________________                                    

Detergents were prepared from the above zeolites in the same manner asdescribed in Example 1, and properties of the resulting detergents weredetermined in the same manner as described in Example 1 to obtainresults shown in Table 26.

                  Table 26                                                        ______________________________________                                                        Sample Sample   Sample                                                        9-4    9-5      9-6                                           ______________________________________                                        Sample Number of Zeolite Used                                                                   9-1      9-2      9-3                                       Washing Power     +2       +1       +0                                        Re-Contamination Preventing                                                                     5        5        5                                         Effect                                                                        Rinsing Property  4.6      4.6      4.5                                       Suspension Stability                                                                            0.3      0.8      1.2                                       Powder Falling Property                                                                         +2       +1       --0                                       ______________________________________                                    

EXAMPLE 10

In this Example, a synthetic zeolite prepared from an alkali metalaluminosilicate slurry was separated from the mother liquor in such astate that a part of excessive sodium hydroxide contained in the motherliquor was incorporated in the zeolite and an acid or acidic salt wasadded to the so separated zeolite composition to effect neutralizationand obtain a synthetic zeolite builder composition.

As the alkali metal aluminosilicate builder containing the alkali metalcomponent, there were chosen the zeolite crystal-containing slurryprepared in Example 1 from which the mother liquor had not beenseparated by filtration (base S), the filter cake formed by removing themother liquor from base S by filtration so that the solid content was50% (base C) and the filter cake formed by washing base C with water onetime (base F). Then, an acid or acidic salt shown in Table 27 was addedto such alkali metal component-containing zeolite composition (base S, Cor F) in an amount indicated in Table 27 (parts by weight per 100 partsby weight of the base as the dried product, and the mixture wassufficiently agitated and blended and dried at about 170° C. by using ahot air drier to form an alkali metal aluminosilicate builder in which apart of the contained alkali metal hydroxide component was neutralizedand combined with the alkali metal component contained. Thus, there wereprepared 34 kinds of such alkali metal silicate binders (samples 10-1 to10-34) as shown in Table 27.

For comparison, an acid (sulfuric acid) was added for neutralization sothat the pH was reduced below 9.0, and the mixture was treated in thesame manner as described above to form comparative sample H-12.

Comparative samples were prepared directly from bases S and C in whichan acid or acidic salt was not incorporated. More specifically, apowdery sample H-10 was prepared by concentrating entirely base Saccording to a customary method for concentrating and solidifyingslurries, drying the concentrate at about 170° C. and pulverizing theresulting solid, and a powdery sample H-11 was prepared by drying base Cat about 170° C. and pulverizing the dried product.

Properties of the foregoing samples were determined in the same manneras described in Example 1 to obtain results shown in Table 27.

                                      Table 2                                     __________________________________________________________________________                             Crystalli-                                                                         Calcium Ion                                                                          Initial                                  Sample              Crystal                                                                            zation                                                                             Binding                                                                              Buffer                                   No.                 Form Degree                                                                             Property(CI)                                                                         Capacity (R)                             __________________________________________________________________________    10-1                                                                              base S + H.sub.2 SO.sub.4 (3 parts)                                                           4A   69.1 130    40.8                                     10-2                                                                              base S + H.sub.3 BO.sub.3 (6 parts)                                                           4A   69.2 135    105.6                                    10-3                                                                              base S + citric acid(3 parts)                                                                 4A   68.3 135    81.8                                     10-4                                                                              base S + citric acid(6 parts)                                                                 4A   66.3 135    105.6                                    10-5                                                                              base S + citric acid(10 parts)                                                                4A   65.2 135    89.7                                     10-6                                                                              base S + H.sub.3 PO.sub.4 (3 parts)                                                           4A   68.4 135    84.4                                     10-7                                                                              base S + H.sub.3 PO.sub.4 (6 parts)                                                           4A   65.0 135    102.9                                    10-8                                                                              base S + H.sub.3 PO.sub.4 (10 parts)                                                          4A   64.2 135    110.8                                    10-9                                                                              base S + polysilicic acid(3 parts)                                                            4A   66.1 130    41.2                                     H-10                                                                              base S          sodalite                                                                           68.2  40    79.8                                                         4A                                                        10-10                                                                             base C + citric acid(3 parts)                                                                 4A   68.8 135    68.6                                     10-11                                                                             base C + citric acid(6 parts)                                                                 4A   66.7 135    63.3                                     10-12                                                                             base C + citric acid(10 parts)                                                                4A   65.4 135    39.6                                     10-13                                                                             base C + H.sub.3 PO.sub.4 (3 parts)                                                           4A   66.2 135    71.3                                     10-14                                                                             base C + H.sub.3 PO.sub.4 (6 parts)                                                           4A   67.1 135    66.0                                     10-15                                                                             base C + polysilicic acid(3 parts)                                                            4A   68.3 130    40.0                                     H-11                                                                              base C          sodalite                                                                           68.6  35    67.1                                                         4A                                                        10-16                                                                             base F + citric acid(1 part)                                                                  4A   69.3 140    50.1                                     10-17                                                                             base F + citric acid(3 parts)                                                                 4A   68.5 140    58.1                                                Effective    Oil   Bulk  Primary                                   Sample                                                                            Buffer Alkali Suspension                                                                          Absorption                                                                          Density                                                                             Particle                                  No. Capacity (S)                                                                         Quantity(Qc)                                                                         pH    (OA)  (BD)  Size(Dp)(μ)                            __________________________________________________________________________    10-1                                                                              160.2  10.4   11.7  51    0.5   0.4                                       10-2                                                                              348.3  13.2   11.6  48    0.49  0.4                                       10-3                                                                              237.5  15.9   12.4  50    0.49  0.4                                       10-4                                                                              348.3  11.4   11.3  48    0.49  0.4                                       10-5                                                                              285.0  12.2   12.1  47    0.49  0.4                                       10-6                                                                              366.8  12.4   11.5  53    0.48  0.4                                       10-7                                                                              345.0  12.2   11.9  49    0.49  0.4                                       10-8                                                                              435.7  9.7    11.0  48    0.49  0.4                                       10-9                                                                              140.1  5.8    10.0  52    0.48  0.4                                       H-10                                                                              200    16.8   12.6  43    0.51  0.4                                       10-10                                                                             192.6  6.5    11.8  54    0.49  0.4                                       10-11                                                                             229.6  5.3    11.0  51    0.49  0.4                                       10-12                                                                             234.9  3.7     9.0  48    0.49  0.4                                       10-13                                                                             237.5  5.2    10.6  55    0.48  0.4                                       10-14                                                                             306.1  4.8     9.0  51    0.48  0.4                                       10-15                                                                             139.3  4.1    10.0  54    0.47  0.4                                       H-11                                                                              184.9  7.3    12.1  40    0.51  0.4                                       10-16                                                                             168.9   3.19  10.6  58    0.47  0.4                                       10-17                                                                             168.9   2.81   9.2  56    0.47  0.4                                           Secondary Particle Size Dis-                                                                 Sedimenta-                                                                           Methylene Blue                                                                         Surface Charge                             Sample                                                                            tribution (Ds) (% by weight)                                                                 tion Speed                                                                           Absorbing                                                                              Controlling                                No. 0-3μ                                                                            3-4μ                                                                            4μ-                                                                             (Vs)   Property (AM)                                                                          Property (ED)                              __________________________________________________________________________    10-1                                                                              91   9    0    0.6    5        4                                          10-2                                                                              93   7    0    0.6    5        4                                          10-3                                                                              93   7    0    0.4    5        4                                          10-4                                                                              95   5    0    0.4    5        4                                          10-5                                                                              97   3    0    0.4    5        4                                          10-6                                                                              100  --   --   0.5    5        4                                          10-7                                                                              100  --   --   0.5    5        4                                          10-8                                                                              100  --   --   0.6    5        4                                          10-9                                                                              92   8    --   0.4    5        4                                          H-10                                                                              90   8    2    0.6    2        4                                          10-10                                                                             90   10   --   0.4    5        4                                          10-11                                                                             89   11   --   0.4    5        4                                          10-12                                                                             89   11   --   0.5    5        4                                          10-13                                                                             98   2    --   0.5    5        4                                          10-14                                                                             100  --   --   0.5    5        4                                          10-15                                                                             93   7    --   0.4    5        4                                          H-11                                                                              91   8    1    0.6      1.5    4                                          10-16                                                                             92   8    0    0.4    5        4                                          10-17                                                                             93   7    0    0.4    5        4                                                                   Crystalli-                                                                         Calcium Ion                                                                          Initial                                  Sample               Crystal                                                                           zation                                                                             Binding                                                                              Buffer                                   No.                  Form                                                                              Degree                                                                             Property(CI)                                                                         Capacity (R)                             __________________________________________________________________________    10-18                                                                             base F + citric acid (5 parts)                                                                 4A  68.5 140    71.3                                     10-19                                                                             base F + citric acid (7 parts)                                                                 4A  68.1 140    63.3                                     10-20                                                                             base F + H.sub.3 PO.sub.4 (1 part)                                                             4A  70.2 140    50.1                                     10-21                                                                             base F +  H.sub.3 PO.sub.4 (5 parts)                                                           4A  68.3 140    42.2                                     H-12                                                                              base F + H.sub.2 SO.sub.4 (1 part)                                                             4A  69.1 126    36.9                                     10-22                                                                             base F + H.sub.3 PO.sub.4 (1 part) + NaOH                                                      4A  69.1 140    47.5                                     10-23                                                                             base F + H.sub.3 PO.sub.4 (3 parts) + NaOH                                                     4A  68.8 140    47.5                                     10-24                                                                             base F + H.sub.3 PO.sub.4 (5 parts) + NaOH                                                     4A  69.1 140    47.5                                     10-25                                                                             base F + H.sub.3 PO.sub.4 (10 parts) + NaOH                                                    4A  67.0 140    47.5                                     10-26                                                                             base F + Na.sub.2 HPO.sub.4 (1 part)                                                           4A  68.2 137    39.6                                     10-27                                                                             base F + Na.sub.2 HPO.sub.4 (3 parts)                                                          4A  68.0 140    39.6                                     10-28                                                                             base F + Na.sub.2 HPO.sub.4 (4.8 parts)                                                        4A  67.1 140    44.9                                     10-29                                                                             base F + NaH.sub.2 PO.sub.4 (1 part)                                                           4A  69.1 139    42.2                                     10-30                                                                             base F + NaH.sub.2 PO.sub.4 (3 parts)                                                          4A  68.5 140    45.5                                     10-31                                                                             base F + NaH.sub.2 PO.sub.4  (4.8 parts)                                                       4A  67.0 138    45.5                                     10-32                                                                             base F + H.sub.3 PO.sub.3 (5 parts) + NaOH                                                     4A  67.1 139    63.3                                     10-33                                                                             base F + H.sub.3 BO.sub.3 (10 parts) + NaOH                                                    4A  67.1 140    71.3                                     10-34                                                                             base F + polysilicic acid (13 parts)                                                           4A  68.0 140    42.0                                                Effective    Oil   Bulk  Primary                                   Sample                                                                            Buffer Alkali Suspension                                                                          Absorption                                                                          Density                                                                             Particle                                  No. Capacity (S)                                                                         Quantity (Qc)                                                                        pH    (OA)  (BD)  Size(Dp)(μ)                            __________________________________________________________________________    10-18                                                                             168.9  2.73    9.15 54    0.48  0.4                                       10-19                                                                             168.9  2.64    9.05 54    0.48  0.4                                       10-20                                                                             163.6  2.57    9.3  58    0.48  0.4                                       10-21                                                                             147.8  2.32    9.1  52    0.48  0.4                                       H-12                                                                              126.7  1.99    8.8  44    0.47  0.4                                       10-22                                                                             155.7  3.64   11.1  52    0.48  0.4                                       10-23                                                                             153.1  3.55   11.1  50    0.47  0.4                                       10-24                                                                             153.1  3.39   11.1  48    0.47  0.4                                       10-25                                                                             153.1  3.43   11.1  48    0.47  0.4                                       10-26                                                                             166.3  3.80   11.0  58    0.48  0.4                                       10-27                                                                             184.7  3.93   10.9  57    0.48  0.4                                       10-28                                                                             195.3  4.05   10.8  54    0.48  0.4                                       10-29                                                                             158.3  3.55   10.6  57    0.48  0.4                                       10-30                                                                             168.9  3.31    9.9  55    0.48  0.4                                       10-31                                                                             190.0  3.06    9.0  55    0.48  0.4                                       10-32                                                                             166.3  4.79   11.1  55    0.48  0.4                                       10-33                                                                             168.9  5.21   11.1  52    0.48  0.4                                       10-34                                                                             142.0  3.2    10.1  53    0.47  0.4                                           Secondary Particle Size Dis-                                                                  Sedimenta-                                                                          Methylene Blue                                                                         Surface Charge                             Sample                                                                            tribution (Ds) (% by weight)                                                                 tion Speed                                                                           Absorbing                                                                              Controlling                                No. 0-3μ                                                                            3-4μ                                                                            4μ-                                                                             (Vs)   Property (AM)                                                                          Property (ED)                              __________________________________________________________________________    10-18                                                                             90   10   0    0.4    5        4                                          10-19                                                                             93   7    0    0.5    5        4                                          10-20                                                                             99   1    0    0.5    5        4                                          10-21                                                                             100  --   --   0.6    5        4                                          H-12                                                                              100  --   --   0.6    5        4                                          10-22                                                                             100  --   --   0.4    5        4                                          10-23                                                                             99   1    --   0.5    5        4                                          10-24                                                                             98   2    --   0.5    5        4                                          10-25                                                                             100  --   --   0.6    5        4                                          10-26                                                                             100  --   --   0.6    5        4                                          10-27                                                                             100  --   --   0.6    5        4                                          10- 28                                                                            99   1    --   0.6    5        4                                          10-29                                                                             99   1    --   0.6    5        4                                          10-30                                                                             100  --   --   0.6    5        4                                          10-31                                                                             100  --   --   0.6    5        4                                          10-32                                                                             98   2    --   0.6    5        4                                          10-33                                                                             98   2    --   0.6    5        4                                          10-34                                                                             95   5    --   0.6    5        4                                          __________________________________________________________________________

By using the above alkali metal aluminosilicate builder samples 10-3,10-6, 10-10, 10-13, 10-16, 10-20, 10-26 and 10-32, detergents (samples10-35 to 10-42) were prepared in the same manner as described in Example1.

Properties of the so prepared detergents were determined in the samemanner as described in Example 1 to obtain results shown in Table 28.

                                      Table 28                                    __________________________________________________________________________                      Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                                                            Sample                                            10-35                                                                             10-36                                                                             10-37                                                                             10-38                                                                             10-39                                                                              -40                                                                              10-41                                                                             10-42                           __________________________________________________________________________    Sample Number of Zeolite Used                                                                   10-3                                                                              10-6                                                                              10-10                                                                             10-13                                                                             10-16                                                                             10-20                                                                             10-26                                                                             10-32                           Washing Power     +2  +2  +2  +2  +2  +2  +2  +2                              Re-Contamination Preventing Effect                                                              5   5   5   5   5   5   5   5                               Rinsing Property  4.3 4.2 4.3 4.4 4.4 4.5 4.4 4.4                             Suspension Stability                                                                            0.4 0.4 0.3 0.3 0.3 0.3 0.3 0.3                             Powder Falling Property                                                                         +2  +2  +2  +2  +2  +2  +2  +2                              __________________________________________________________________________

EXAMPLE 11

This Example illustrates a builder composition prepared by separating asynthetic zeolite crystallized out at the step of preparing an alkalimetal aluminosilicate builder from the mother liquor in a state where apart of excessive sodium hydroxide contained in the mother liquor isincluded into the zeolite, adding phosphoric acid (H₃ PO₄) to therecovered zeolite composition and drying and calcining the resultingmixture, and a builder composition prepared by washing the above zeoliteseparated from the mother liquor with water, adding disodiumhydrogenphosphate (Na₂ HPO₄) to the washed zeolite and drying andcalcining the resulting mixture.

Run (A)

A 5% solution of commerically available phosphoric acid was added tobase C described in Example 10 so that the pH was reduced to 10, and theresulting slurry composition was dried in a drier maintained at 110° C.,calcined at 500° C. for 1 hour in an electric furnace and pulverized toobtain a powdery sample (sample 11-1).

Run (B)

To 100 g of base F described in Example 10 was added a 10% solution ofdisodium hydrogen phosphate in an amount, as Na₂ HPO₄, corresponding to10% by weight based on the zeolite, and the mixture was dried in a driermaintained at 110° C., calcined at 500° C. for 1 hour in an electricfurnace and pulverized to obtain a powdery sample (sample 11-2).

Properties of the so prepared samples were determined in the same manneras described in Example 1 to obtain results shown in Table 29.

                  Table 29                                                        ______________________________________                                                           Sample     Sample                                          Item               11-1       11-2                                            ______________________________________                                        Crystal Form       A+sodium   A+sodium                                                           phosphate  phosphate                                       Crystallization Degree (CR)                                                                      67         70                                              Calcium Ion Binding Property (CI)                                                                170        183                                             Initial Buffer Capacity (R)                                                                      76         57                                              Buffer Capacity (S)                                                                              192        200                                             Effective Alkali Quantity (Qc)                                                                   3.9        5.2                                             Suspension pH      10.1       10.6                                            Oil Absorption (OA)                                                                              45         45                                              Bulk Density (BD)  0.45       0.45                                            Primary Particle Size (Dp) (μ)                                                                0.4        0.4                                             Secondary Particle Size Distribu-                                             tion (Ds) (% by weight)                                                       0 - 3 μ         97         96.2                                            3 - 4 μ         3          3.8                                             4 μ -           0          0                                               Sedimentation Speed (Vs)                                                                         0.3        0.3                                             Surface Charge Controlling                                                                       4          4                                               Property (ED)                                                                 ______________________________________                                    

Detergents were prepared in the same manner as described in Example 1 byusing the above samples 11-1 and 11-2, and properties of the resultingdetergents (samples 11-3 and 11-4) were determined in the same manner asdescribed in Example 1 to obtain results shown in Table 30.

                  Table 30                                                        ______________________________________                                                           Sample  Sample                                                                11-3    11-4                                               ______________________________________                                        Sample Number of Zeolite Used                                                                      11-1      11-2                                           Washing Power        +2        +2                                             Re-Contamination Preventing                                                                        5         5                                              Effect                                                                        Rinsing Power        4.6       4.6                                            Suspension Stability 0.3       0.3                                            Powder Falling Property                                                                            +2        +2                                             ______________________________________                                    

EXAMPLE 12

In this Example, zeolite builders prepared according to this inventionwere incorporated in detergents having a practical composition, and theresulting detergents were subjected to tests using contaminated clothsfor determination of the washing power, recontamination preventingeffect, rinsing property, suspension stability and powder fallingproperty. Practical detergent compositions adopted in this Example areillustrated in Tables 31 to 33.

                  Table 31                                                        ______________________________________                                        Composition A                                                                                           Parts by                                            Components                Weight                                              ______________________________________                                        Anionic Surface Active Agents                                                  LAS (linear alkyl benzene-sulfonate)                                                                   10                                                   AOS (α-olefin sulfonate)                                                                         8                                                   Non-Ionic Surface Active Agent                                                 Polyethylene glycol fatty acid ester                                                                   1                                                   Builder*                  20                                                  Sodium Silicate           5                                                   Sodium Carbonate          3                                                   CMC (carboxymethylcellulose)                                                                            1                                                   Sodium Sulfate            50                                                  Water                     10                                                  ______________________________________                                    

                  Table 32                                                        ______________________________________                                        Composition B                                                                                           Parts by                                            Components                Weight                                              ______________________________________                                        Anionic Surface Active Agents                                                  LAS (linear alkyl benzene-sulfonate)                                                                   10                                                   AS (alcohol sulfate)     5                                                    AES (alcohol ether sulfate)                                                                            3                                                   Non-Ionic Surface Active Agent                                                 Alcohol polyoxyethylene ether                                                                          2                                                   Builder*                  20                                                  Sodium Silicate           5                                                   Sodium Carbonate          3                                                   CMC (carboxymethylcellulose)                                                                            1                                                   Sodium Sulfate            50                                                  Water                     10                                                  ______________________________________                                    

                  Table 33                                                        ______________________________________                                        Composition C                                                                                           Parts by                                            Components                Weight                                              ______________________________________                                        Anionic Surface Active Agent                                                   LAS (linear alkyl benzene-sulfonate)                                                                    2                                                  Non-Ionic Surface Active Agent                                                 Alkylphenyl polyoxyethylene ether                                                                      18                                                  Builder*                  20                                                  Sodium Silicate            5                                                  Sodium Carbonate           5                                                  CMC (carboxymethylcellulose)                                                                             1                                                  Sodium Sulfate            30                                                  Sodium Perborate          10                                                  Water                     10                                                  ______________________________________                                    

As the builder asteriked, there were used those shown in the foregoingExamples and commercially available sodium tripolyphosphate (Na₅ P₃ O₁₀)as a control.

Obtained results are shown in Tables 34, 35 and 36.

                                      Table 34                                    __________________________________________________________________________    Composition A                                                                 Sample Number of  Re-Contamination                                                                       Rinsing                                                                            Suspension                                                                          Powder Falling                          Builder Used                                                                            Washing Power                                                                         Preventing Effect                                                                      Property                                                                           Stability                                                                           Property                                __________________________________________________________________________    1 - 3     +2      5        4.6  0.3   +2                                      2 - 7     +2      5        4.6  0.2   +1                                      3 - 1     +2      5        4.6  0.4   +2                                      4 - 5     +2      5        4.6  0.3   +2                                      8 - 1     +2      5        4.5  0.3   +2                                      H - 3     -2      2        1.2  18    -2                                      H - 7     -2      1        1.0  37.4  -2                                      Sodium tripolyphos-                                                                     0       5        4.6  --    +2                                      phate                                                                         __________________________________________________________________________

                                      Table 35                                    __________________________________________________________________________    Composition B                                                                 Sample Number of  Re-Contamination                                                                       Rinsing                                                                            Suspension                                                                          Powder Falling                          Builder Used                                                                            Washing Power                                                                         Preventing Effect                                                                      Property                                                                           Stability                                                                           Property                                __________________________________________________________________________    1 - 3     +2      5        4.6  0.3   +2                                      5 - 7     +2      5        4.5  0.3   +2                                      6 - 4     +1      5        4.4  0.4   +1                                      7 - 4     +2      5        4.7  0.3   +2                                      8 - 1     +2      5        4.5  0.3   +2                                      H - 6     -2      3        1.2  16    -2                                      H - 7     -2      1        1    37    -2                                      Sodium tripolyphos-                                                                     0       5        4.6        +2                                      phate                                                                         __________________________________________________________________________

                                      Table 36                                    __________________________________________________________________________    Composition C                                                                 Sample Number of  Re-Contamination                                                                       Rinsing                                                                            Suspension                                                                          Powder Falling                          Builder Used                                                                            Washing Power                                                                         Preventing Effect                                                                      Property                                                                           Stability                                                                           Property                                __________________________________________________________________________    2 - 7     +2      5        4.6  0.2   +1                                      3 - 1     +2      5        4.6  0.4   +2                                      5 - 7     +2      5        4.5  0.3   +2                                      6 - 4     +1      5        4.4  0.4   +1                                      7 - 4     +2      5        4.7  0.3   +2                                      H - 2     -2      3        1.4  14    -2                                      H - 6     -2      3        1.2  15    -2                                      Sodium tripolyphos-                                                                     0       5        4.6        +2                                      phate                                                                         __________________________________________________________________________

EXAMPLE 13

In This Example, builders prepared in the foregoing Examples wereincorporated in a liquid detergent having a practical composition, andthe suspension stability of the resulting detergents was tested. Thecomposition of the liquid detergent is shown in Table 37 and testresults are shown in Table 38

                  Table 37                                                        ______________________________________                                        Liquid Detergent Composition                                                                          Parts by                                              Components              Weight                                                ______________________________________                                        Anionic Surface Active Agent                                                  LAS (linear alkyl benzene-sulfonate)                                                                  20                                                    Non-Ionic Surface Active Agent                                                Alcohol polyoxyethylene ether                                                                          1                                                    Ethanol                  7                                                    CMC (carboxymethylcellulose)                                                                           1                                                    Water                   70                                                    Builder*                20                                                    ______________________________________                                    

                  Table 38                                                        ______________________________________                                        Sample Number of Builder Used                                                                     Suspension Stability                                      ______________________________________                                        1 - 3               0.2                                                       2 - 7               0.3                                                       3 - 1               0.2                                                       8 - 1               0.1                                                       H - 3               15                                                        ______________________________________                                    

From the results shown in Table 38, fine synthetic zeolite buildersprepared according to this invention provide detergents excellent in thesuspension stability, and the builders of this invention are veryvaluable.

EXAMPLE 14

In this Example, a synthetic zeolite builder (sample 1-3) wasincorporated into a commercially available solid cosmetic soapcomposition as indicated in Table 39, and properties of the resultingsoap were compared with those of a commercially available cosmetic soapby a panel of 5 experts to obtain results shown in Table 40.

                  Table 39                                                        ______________________________________                                        Component              Parts by Weight                                        ______________________________________                                        Commercially available solid cosmetic                                                                70                                                     soap                                                                          Builder of this invention (sample 1-3)                                                               30                                                     Water                  20                                                     ______________________________________                                    

                  Table 40                                                        ______________________________________                                                     Evaluation by Panel of 5 Experts                                 ______________________________________                                        Touch to skin  comparable to commercially avail-                                             able soap                                                      Touch to hand     "                                                           Washing power  superior to commercially available                                            soap                                                           Bubbline property                                                                               "                                                           Generic evaluation                                                                              "                                                           ______________________________________                                    

As will readily be understood from the above results, a soap comprisingthe builder of this invention is comparable or superior to acommercially available cosmetic soap with respect to properties requiredof cosmetic soaps.

What we claim is:
 1. A process for the preparation of detergent builderswhich comprises acid-treating a smectite clay mineral under suchconditions that at least the X-ray diffraction peak of the plane index(001) substantially disappears and removing a basic metal component inthe reaction product by extraction to thereby prepare activated silicaor activated alumina-silica, treating the so prepared activated silicaor activated alumina-silica with an alkali metal hydroxide or awater-soluble alkali metal silicate to prepare an alkali metalpolysilicate or alkali metal polyaluminosilicate having a composition inwhich the Na₂ O/SiO₂ molar ratio is in the range of from 1/3.5 to 1/500,mixing said alkali metal polysilicate or alkali metalpolyaluminosilicate with additional amounts of alumina and alkali metalcomponents and water to prepare a homogeneous mixture having acomposition capable of forming zeolite of the type A, and heating saidhomogeneous mixture to crystallize out fine zeolitic particles having amaximum primary particle size smaller than 1 μ.
 2. A process for thepreparation of detergent builders according to claim 1 wherein thesmectite clay mineral is a montmorillonite clay mineral.
 3. A processfor the preparation of detergent builders according to claim 1 whereinthe smectite clay mineral is acid-treated so that the height of theX-ray diffraction peak of the plane index [001] of the acid-treated clayis less than 1%, of the height of the X-ray diffraction peak of theplane index [001] of the starting smectite clay mineral.
 4. A processfor the preparation of detergent builders according to claim 1 whereinthe smectite clay mineral is acid-treated so that the height of theX-ray diffraction peak of the plane index [001] [020] of theacid-treated clay is less than 15% of the height of the X-raydiffraction peak of the plane index [110] [020] of the starting smectiteclay mineral.
 5. A process for the preparation of detergent buildersaccording to claim 1 wherein the smectite clay mineral is acid-treatedso that the acid-treated clay has an aromatic adsorption index (AAI) ofat least
 16. 6. A process for the preparation of detergent buildersaccording to claim 1 wherein said activated silica or activatedalumina-silica is treated with an alkali metal hydroxide or awater-soluble alkali metal silicate to form an alkali metal polysilicateor alkali metal polyaluminosilicate having a composition in which theNa₂ O/SiO₂ molar ratio is in the range of from 1/4 to 1/400.
 7. Aprocess for the preparation of detergent builders according to claim 1wherein said activated silica or activated alumina-silica is treatedwith an alkali metal hydroxide or a water-soluble alkali metal silicatein the presence of water in an amount of 1 to 49 parts by weight ofwater per part by weight of said activated silica or activatedalumina-silica.
 8. A process for the preparation of detergent buildersaccording to claim 1 wherein an aqueous mixture of said activated silicaor activated alumina-silica and said alkali metal hydroxide orwater-soluble alkali metal silicate is aged for at least 0.2 hour.
 9. Aprocess for the preparation of detergent builders according to claim 1wherein the particle size of said alkali metal polysilicate or alkalimetal polyaluminosilicate is adjusted so that particles having a sizesmaller than 5 μ occupy at least 20% by weight of the total particlesand particles having a particle size larger than 20 μ occupy less than30% by weight of the total particles.
 10. A process for the preparationof detergent builders according to claim 9 wherein said particle sizeadjustment is carried out in at least one stage of said process prior toheating said homogeneous mixture.
 11. A process for the preparation ofdetergent builders according to claim 1 wherein said alkali metalpolysilicate or alkali metal aluminosilicate is mixed with additionalamounts of alumina and alkali metal components and water to form ahomogeneous admixture having a composition in which the SiO₂ /Al₂ O₃molar ratio based on the oxides is in the range of from 0.1 to 3.5, theNa₂ O/SiO₂ molar ratio based on the oxides is in the range of from 0.5to 5 and the H₂ O/Na₂ O molar ratio based on the oxides is in the rangeof from 15 to
 150. 12. A process for the preparation of detergentbuilders according to claim 11 wherein said homogeneous admixture isformed by adding an alkaline aqueous solution of an alkali metalaluminate to an aqueous dispersion of said alkali metal polysilicate oralkali metal polyaluminosilicate.
 13. A process for the preparation ofdetergent builders according to claim 1 wherein the alkali concentration(as expressed as mole % of Na₂ O) in the homogeneous admixture is in therange of 0.25 to 7 mole %.
 14. A process for the preparation ofdetergent builders according to claim 1 wherein zeolite is crystallizedout by heating said homogeneous admixture under conditions satisfyingthe following requirements: ##EQU10## wherein t stands for thecrystallizing-out time (hr), T stands for the crystallizing-outtemperature (° K, absolute temperature), and CA stands for an alkaliconcentration (mole %) in the zeolite-forming homogeneous admixture. 15.A process for the preparation of detergent builders according to claim 3wherein the smectite clay mineral is acid-treated so that the height ofthe X-ray diffraction peak of the plane index [001] of the acid-treatedclay is less than 5% of the height of the X-ray diffraction peak of theplane index (001) of the starting smectite clay mineral.
 16. A processfor the preparation of detergent builders according to claim 4 whereinthe smectite clay mineral is acid-treated so that the height of theX-ray diffraction peak of the plane index [001][020] of the acid-treatedclay is less than 5% of the height of the X-ray diffraction peak of theplane index [110][020] of the starting smectite clay mineral.
 17. Aprocess for the preparation of detergent builders according to claim 5wherein the smectite clay mineral is acid-treated so that theacid-treated clay has an aromatic adsorption index (AAI) of at least 20to
 60. 18. A process for the preparation of detergent builders accordingto claim 6 wherein said activated silica or activated alumina-silica istreated with an alkali metal hydroxide or a water-soluble alkali metalsilicate to form an alkali metal polysilicate or alkali metalpolyaluminosilicate having a composition in which the Na₂ O/SiO₂ molarratio is in the range of from 1/7 to 1/300.
 19. A process for thepreparation of detergent builders according to claim 7 wherein saidactivated silica or activated alumina-silica is treated with an alkalimetal hydroxide or a water-soluble alkali metal silicate in the presenceof water in an amount of 2 to 9 parts by weight of water per part byweight of said activated silica or activated alumina-silica.
 20. Aprocess for the preparation of detergent builders according to claim 8wherein an aqueous mixture of said activated silica or activatedalumina-silica and said alkali metal hydroxide or water-soluble alkalimetal silicate is aged for at least 2 hours.
 21. A process for thepreparation of detergent builders according to claim 9 wherein theparticle size of said alkali metal polysilicate or alkali metalpolyaluminosilicate is adjusted so that particles having a size smallerthan 5 μ occupy at least 50% by weight of the total particles andparticles having a particle size larger than 20 μ occupy less than 10%by weight of the total particles.
 22. A process for the preparation ofdetergent builders according to claim 10 wherein said particle sizeadjustment is carried out before the alkali treatment.